Layer Protecting the Surface of Zirconium Used in Nuclear Reactors.

PubMed

Ashcheulov, Petr; Skoda, Radek; Skarohlíd, Jan; Taylor, Andrew; Fendrych, Frantisek; Kratochvílová, Irena

2016-01-01

Zirconium alloys have very useful properties for nuclear facilities applications having low absorption cross-section of thermal electrons, high ductility, hardness and corrosion resistance. However, there is also a significant disadvantage: it reacts with water steam and during this (oxidative) reaction it releases hydrogen gas, which partly diffuses into the alloy forming zirconium hydrides. A new strategy for surface protection of zirconium alloys against undesirable oxidation in nuclear reactors by polycrystalline diamond film has been patented- Czech patent 305059: Layer protecting the surface of zirconium alloys used in nuclear reactors and PCT patent: Layer for protecting surface of zirconium alloys (Patent Number: WO2015039636-A1). The zirconium alloy surface was covered by polycrystalline diamond layer grown in plasma enhanced chemical vapor deposition apparatus with linear antenna delivery system. Substantial progress in the description and understanding of the polycrystalline diamond/ zirconium alloys interface and material properties under standard and nuclear reactors conditions (irradiation, hot steam oxidation experiments and heating-quenching cycles) was made. In addition, process technology for the deposition of protective polycrystalline diamond films onto the surface of zirconium alloys was optimized. Zircaloy2 nuclear fuel pins were covered by 300 nm thick protective polycrystalline diamond layer (PCD) using plasma enhanced chemical vapor deposition apparatus with linear antenna delivery system. The polycrystalline diamond layer protects the zirconium alloy surface against undesirable oxidation and consolidates its chemical stability while preserving its functionality. PCD covered Zircaloy2 and standard Zircaloy2 pins were for 30 min. oxidized in 1100°C hot steam. Under these conditions α phase of zirconium changes to β phase (more opened for oxygen/hydrogen diffusion). PCD anticorrosion protection of Zircaloy nuclear fuel assemblies can

Clinical Outcomes of Zirconium-Oxide Posts: Up-to-Date Systematic Review.

PubMed

Al-Thobity, Ahmad M

2016-06-01

The aim of this systematic review was to investigate the clinical outcomes of the use of zirconium-oxide posts in the past 20 years. The addressed question was: Do zirconium-oxide posts maintain the long-term survival rate of endodontically treated teeth? A database search was made of articles from January 1995 to December 2014; it included combinations of the following keywords: "zirconia," "zirconium oxide," "dowel/dowels," "post/posts," and "post and core." Exclusion criteria included review articles, experimental studies, case reports, commentaries, and articles published in a language other than English. Articles were reviewed by the titles, followed by the abstracts, and, finally, the full text of the selected studies. Four studies were included after filtering the selected studies according to the inclusion and exclusion criteria. In one study, the prefabricated zirconia posts with indirect glass-ceramic cores had significantly higher failure rates than other posts with direct composite cores. In two studies, no failure of the cemented posts was observed throughout the follow-up period. Due to the limited number of clinical studies, it can be concluded that the long-term success rate of prefabricated zirconium-oxide posts is unclear.

Novel one-pot synthesis of dicarboxylic acids mediated alginate-zirconium biopolymeric complex for defluoridation of water.

PubMed

Prabhu, Subbaiah Muthu; Meenakshi, Sankaran

2015-04-20

The present investigation explains the fluoride removal from aqueous solution using alginate-zirconium complex prepared with respective dicarboxylic acids like oxalic acid (Ox), malonic acid (MA) and succinic acid (SA) as a medium. The complexes viz., alginate-oxalic acid-zirconium (Alg-Ox-Zr), alginate-malonic acid-zirconium (Alg-MA-Zr) and alginate-succinic acid-zirconium (Alg-SA-Zr) were synthesized and studied for fluoride removal. The synthesized complexes were characterized by FTIR, XRD, SEM with EDAX and mapping images. The effects of various operating parameters were optimized. The result showed that the maximum removal of fluoride 9653mgF(-)/kg was achieved by Alg-Ox-Zr complex at acidic pH in an ambient atmospheric condition. Equilibrium data of Alg-Ox-Zr complex was fitted well with Freundlich isotherm. The calculated values of thermodynamic parameters indicated that the fluoride adsorption is spontaneous and endothermic in nature. The mechanism of fluoride removal behind Alg-Ox-Zr complex has been proposed in detail. The suitability of the Alg-Ox-Zr complex has been tested with the field sample collected in a nearby fluoride endemic area. Copyright © 2014 Elsevier Ltd. All rights reserved.

Using Yttra-Stabilized Zirconium Oxide Ceramics to Sense pH and Oxygen in Hydrothermal and Geothermal Applications

NASA Astrophysics Data System (ADS)

Manna, M. F.; Grandstaff, D. E.; Ulmer, G. C.

2002-05-01

Zirconium-Oxide ceramics stabilized with ~8-wt% Yttrium-Oxide can be employed to sense pH in high temperature (>90oC) aqueous environments with an accuracy of 0.05 pH log units (Lvov et al., in press), and to sense the fugacity of oxygen (fO2) in low temperature (>230oC) gaseous environments with an accuracy of 0.2 (fO2) log units. The major components, in two commercially available yttria-stabilized ceramics are yttria ( ~8-wt%) and zirconia ( ~91-wt%) with minor amounts of Ti, Fe and U. The textural differences in the two ceramics produces significantly different emf vs. 10,000/T responses. Response error can be introduced by: the ionic contribution of the softening glass, the catalytic action of the Pt sensor components, and the presence of Ti and Fe in the ceramic, which has been shown to alter the oxygen diffusivity of the ceramic. (Merino et al., 1996) The first type of ceramic contains a 3-dimensionally-continuous Ca-Al-Si feldspathic glass that acts as a sintering aid during manufacturing. The glass, which has a higher ionic conductivity than the zirconia ceramic, reduces the bulk resistivity and induces an error over the temperature ranges representing the softening point of the glass. The glass also reduces durability of the ceramic. When the glass hydrates it produces zeolites, which grow primarily in the triple-grain-junctions of the ceramic. Thus mechanically weakening the ceramic generating electronic, ionic and mechanical stability problems. The second type of ceramic contains no grain boundary glass, but does contain discrete silicate phases (such as diopside, wollastonite, periclase, silica, etc.) in the triple-grain-junctions. Because there is no inter-granular glass, the type two ceramic does have a greater bulk resistivity compared with the type one ceramic. In a gas-sensing configuration, resistivity has been shown to affect the minimum temperature of sensor operation. A sensor with a higher bulk resistivity must reach a higher minimum

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Artefacts in multimodal imaging of titanium, zirconium and binary titanium–zirconium alloy dental implants: an in vitro study

PubMed Central

Schöllchen, Maximilian; Aarabi, Ghazal; Assaf, Alexandre T; Rendenbach, Carsten; Beck-Broichsitter, Benedicta; Semmusch, Jan; Sedlacik, Jan; Heiland, Max; Fiehler, Jens; Siemonsen, Susanne

2017-01-01

Objectives: To analyze and evaluate imaging artefacts induced by zirconium, titanium and titanium–zirconium alloy dental implants. Methods: Zirconium, titanium and titanium–zirconium alloy implants were embedded in gelatin and MRI, CT and CBCT were performed. Standard protocols were used for each modality. For MRI, line–distance profiles were plotted to quantify the accuracy of size determination. For CT and CBCT, six shells surrounding the implant were defined every 0.5 cm from the implant surface and histogram parameters were determined for each shell. Results: While titanium and titanium–zirconium alloy induced extensive signal voids in MRI owing to strong susceptibility, zirconium implants were clearly definable with only minor distortion artefacts. For titanium and titanium–zirconium alloy, the MR signal was attenuated up to 14.1 mm from the implant. In CT, titanium and titanium–zirconium alloy resulted in less streak artefacts in comparison with zirconium. In CBCT, titanium–zirconium alloy induced more severe artefacts than zirconium and titanium. Conclusions: MRI allows for an excellent image contrast and limited artefacts in patients with zirconium implants. CT and CBCT examinations are less affected by artefacts from titanium and titanium–zirconium alloy implants compared with MRI. The knowledge about differences of artefacts through different implant materials and image modalities might help support clinical decisions for the choice of implant material or imaging device in the clinical setting. PMID:27910719

Artefacts in multimodal imaging of titanium, zirconium and binary titanium-zirconium alloy dental implants: an in vitro study.

PubMed

Smeets, Ralf; Schöllchen, Maximilian; Gauer, Tobias; Aarabi, Ghazal; Assaf, Alexandre T; Rendenbach, Carsten; Beck-Broichsitter, Benedicta; Semmusch, Jan; Sedlacik, Jan; Heiland, Max; Fiehler, Jens; Siemonsen, Susanne

2017-02-01

To analyze and evaluate imaging artefacts induced by zirconium, titanium and titanium-zirconium alloy dental implants. Zirconium, titanium and titanium-zirconium alloy implants were embedded in gelatin and MRI, CT and CBCT were performed. Standard protocols were used for each modality. For MRI, line-distance profiles were plotted to quantify the accuracy of size determination. For CT and CBCT, six shells surrounding the implant were defined every 0.5 cm from the implant surface and histogram parameters were determined for each shell. While titanium and titanium-zirconium alloy induced extensive signal voids in MRI owing to strong susceptibility, zirconium implants were clearly definable with only minor distortion artefacts. For titanium and titanium-zirconium alloy, the MR signal was attenuated up to 14.1 mm from the implant. In CT, titanium and titanium-zirconium alloy resulted in less streak artefacts in comparison with zirconium. In CBCT, titanium-zirconium alloy induced more severe artefacts than zirconium and titanium. MRI allows for an excellent image contrast and limited artefacts in patients with zirconium implants. CT and CBCT examinations are less affected by artefacts from titanium and titanium-zirconium alloy implants compared with MRI. The knowledge about differences of artefacts through different implant materials and image modalities might help support clinical decisions for the choice of implant material or imaging device in the clinical setting.

Selective identification of specialized pro-resolving lipid mediators from their biosynthetic double di-oxygenation isomers.

PubMed

Hansen, Trond V; Dalli, Jesmond; Serhan, Charles N

The n-3 polyunsaturated fatty acids are substrates for lipoxygenases and cyclooxygenases. During inflammatory processes, these enzymes form several distinct families of oxygenated polyunsaturated fatty acids coined specialized pro-resolving lipid mediators. Structural elucidation of these natural products using LC-MS/MS based metabololipidomics with the pico- to nanogram amounts of biosynthetic material available have been performed. The specialized pro-resolving lipid mediators display stereospecific and potent anti-inflammatory and pro-resolving actions. Most often the different families among these mediators are chemically characterized by two or three chiral, secondary alcohols, separated by either an E,E,Z -triene or an E,Z,E,E -tetraenemoiety. The lipoxygenases also form other oxygenated polyunsaturated natural products, coined double di-oxygenation products, that are constitutional isomers of the protectin and maresin families of specialized pro-resolving lipid mediators. Very often these products exhibit similar chromatographic properties and mass spectrometrical fragment ions as the pro-resolving mediators. In addition, the double di-oxygenation products are sometimes formed in larger amounts than the specialized pro-resolving lipid mediators. Thus, it is not always possible to distinguish between the specialized pro-resolving mediators and their double di-oxygenation isomers in biological systems, using LC/MS-based techniques. Herein, a convenient and easy-to-use protocol to meet this challenge is presented.

Kinetic modeling of α-hydrogen abstractions from unsaturated and saturated oxygenate compounds by carbon-centered radicals.

PubMed

Paraskevas, Paschalis D; Sabbe, Maarten K; Reyniers, Marie-Françoise; Papayannakos, Nikos; Marin, Guy B

2014-06-23

Hydrogen abstractions are important elementary reactions in a variety of reacting media at high temperatures in which oxygenates and hydrocarbon radicals are present. Accurate kinetic data are obtained from CBS-QB3 ab initio (AI) calculations by using conventional transition-state theory within the high-pressure limit, including corrections for hindered rotation and tunneling. From the obtained results, a group-additive (GA) model is developed that allows the Arrhenius parameters and rate coefficients for abstraction of the α-hydrogen from a wide range of oxygenate compounds to be predicted at temperatures ranging from 300 to 1500 K. From a training set of 60 hydrogen abstractions from oxygenates by carbon-centered radicals, 15 GA values (ΔGAV°s) are obtained for both the forward and reverse reactions. Among them, four ΔGAV°s refer to primary contributions, and the remaining 11 ΔGAV°s refer to secondary ones. The accuracy of the model is further improved by introducing seven corrections for cross-resonance stabilization of the transition state from an additional set of 43 reactions. The determined ΔGAV°s are validated upon a test set of AI data for 17 reactions. The mean absolute deviation of the pre-exponential factors (log A) and activation energies (E(a)) for the forward reaction at 300 K are 0.238 log(m(3)  mol(-1)  s(-1)) and 1.5 kJ mol(-1), respectively, whereas the mean factor of deviation <ρ> between the GA-predicted and the AI-calculated rate coefficients is 1.6. In comparison with a compilation of 33 experimental rate coefficients, the <ρ> between the GA-predicted values and these experimental values is only 2.2. Hence, the constructed GA model can be reliably used in the prediction of the kinetics of α-hydrogen-abstraction reactions between a broad range of oxygenates and oxygenate radicals. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of making crack-free zirconium hydride

DOEpatents

Sullivan, Richard W.

1980-01-01

Crack-free hydrides of zirconium and zirconium-uranium alloys are produced by alloying the zirconium or zirconium-uranium alloy with beryllium, or nickel, or beryllium and scandium, or nickel and scandium, or beryllium and nickel, or beryllium, nickel and scandium and thereafter hydriding.

ASRDI oxygen technology survey. Volume 3: Heat transfer and fluid dynamics. Abstracts of selected technical reports and publications

NASA Technical Reports Server (NTRS)

Schmidt, A. F. (Editor)

1972-01-01

Selected information is presented from an assemblage of reports and publications on heat transfer and fluid dynamics with direct applicability to oxygen systems. For each document cited, an abstract has been prepared together with key words and a listing of most important references found in the document. Additionally, an author index, a subject index, and a key word index have been provided to simplify the retrieval of specific information from this work. In each subject area - e.g., boiling heat transfer - the individual citations are listed alphabetically by first author, with review papers dually noted under the appropriate subject category and under review papers. Of the documents reviewed and evaluated for inclusion in this publication, coverage of existing information directly concerned with oxygen was given primary emphasis. However, work not specifically oxygen-designated but considered applicable to oxygen by the reviewer e.g., a two-phase friction factor correlation derived from nitrogen experiments is occasionally given where no actual oxygen data exist, as an aid to the reader. Approximately 130 abstracts are listed.

Modification in band gap of zirconium complexes

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

Sharma, Mayank, E-mail: mayank30134@gmail.com; Singh, J.; Chouhan, S.

2016-05-06

The optical properties of zirconium complexes with amino acid based Schiff bases are reported here. The zirconium complexes show interesting stereo chemical features, which are applicable in organometallic and organic synthesis as well as in catalysis. The band gaps of both Schiff bases and zirconium complexes were obtained by UV-Visible spectroscopy. It was found that the band gap of zirconium complexes has been modified after adding zirconium compound to the Schiff bases.

SEPARATION PROCESS FOR ZIRCONIUM AND COMPOUNDS THEREOF

DOEpatents

Crandall, H.W.; Thomas, J.R.

1959-06-30

The separation of zirconium from columbium, rare earths, yttrium and the alkaline earth metals, such mixtures of elements occurring in zirconium ores or neutron irradiated uranium is described. According to the invention a suitable separation of zirconium from a one normal acidic aqueous solution containing salts, nitrates for example, of tetravalent zirconium, pentavalent columbium, yttrium, rare earths in the trivalent state and alkaline earths can be obtained by contacting the aqueous solution with a fluorinated beta diketonc alone or in an organic solvent solution, such as benzene, to form a zirconium chelate compound. When the organic solvent is present the zirconium chelate compound is directly extracted; otherwise it is separated by filtration. The zirconium may be recovered from contacting the organic solvent solution containing the chelated compound by back extraction with either an aqueous hydrofluoric acid or an oxalic acid solution.

THE ANALYSIS OF URANIUM-ZIRCONIUM ALLOYS

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

Milner, G.W.C.; Skewies, A.F.

1953-03-01

A satisfactory procedure is described for the analysis of uranium-zirconium alloys containing up to 25% zirconium. It is based on the separation of the zirconium from the uranium by dissolving the cupferron complex of the former element into chloroform. After the evaporation of the solvent from the combined organic extracts, the residue is ignited to zirconium oxide. The latter is then re-dissolved and zirconium is separated from other elements co-extracted in the solvent extraction procedure by precipitation with mandelic acid. The zirconium mandelate is finally ignited to oxide at 960 deg C. The uranium is separated from the aqueous solutionmore » remaining from the cupferron extraction by precipitating with tannin at a pH of 8; the precipitate being removed by filtration and then ignited a t 800 deg C. The residue is dissolved in nitric acid and the uranium is finally determined by precipitating as ammonium diuranate and then igniting to U{sub 3}O{sub 8}. (auth)« less

Ablation Resistant Zirconium and Hafnium Ceramics

NASA Technical Reports Server (NTRS)

Bull, Jeffrey (Inventor); White, Michael J. (Inventor); Kaufman, Larry (Inventor)

1998-01-01

High temperature ablation resistant ceramic composites have been made. These ceramics are composites of zirconium diboride and zirconium carbide with silicon carbide, hafnium diboride and hafnium carbide with silicon carbide and ceramic composites which contain mixed diborides and/or carbides of zirconium and hafnium. along with silicon carbide.

Method for preparing hydrous zirconium oxide gels and spherules

DOEpatents

Collins, Jack L.

2003-08-05

Methods for preparing hydrous zirconium oxide spherules, hydrous zirconium oxide gels such as gel slabs, films, capillary and electrophoresis gels, zirconium monohydrogen phosphate spherules, hydrous zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite sorbent, zirconium monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite, hydrous zirconium oxide fiber materials, zirconium oxide fiber materials, hydrous zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite and spherules of barium zirconate. The hydrous zirconium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process are useful as inorganic ion exchangers, catalysts, getters and ceramics.

Translucency and Strength of High Translucency Monolithic Zirconium Oxide Materials

DTIC Science & Technology

2016-05-17

Zirconium-Oxide Materials presented at/published to the Journal of General Dentistry with MDWI 41-108, and has been assigned local file #16208. 2...PUBLISHED/PRESENTED. D 11a. PUBLICATION/JOURNAL (list intended publication/journal.) General Dentistry D 11b. PUBLISHED ABSTRACT (List intended...the most esthetic full veneer restorative material in dentistry for many years. In the mid-1900’s, dental materials researchers began marketing and

Fine-grained zirconium-base material

DOEpatents

Van Houten, G.R.

1974-01-01

A method is described for making zirconium with inhibited grain growth characteristics, by the process of vacuum melting the zirconium, adding 0.3 to 0.5% carbon, stirring, homogenizing, and cooling. (Official Gazette)

Effect of oxidation on transport properties of zirconium-1% niobium alloy

NASA Astrophysics Data System (ADS)

Peletsky, V. E.; Musayeva, Z. A.

1995-11-01

The thermal conductivity and electrical resistivity of zirconium-1 wt% niobium samples were measured before and after the process of their oxidation in air. A special procedure was used to dissolve the gas and to smooth out its concentration in the alloy. The basic experiments were performed under high vacuum under steady-state temperature conditions. The temperature range was 300 1600 K. for the pure alloy and 300 1100 K for the samples containing oxygen. It was found that the thermal conductivity—oxygen concentration relation reverses its sign from negative at low and middle temperatures to positive at temperatures above 900 K. The relation between the electrical resistivity and the oxygen content does not show this feature. The Lorenz function was found to have an anomalous temperature dependence.

SEPARATION OF HAFNIUM FROM ZIRCONIUM

DOEpatents

Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

1960-05-31

The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

Zirconium

USGS Publications Warehouse

Bedinger, G.M.

2013-01-01

Zirconium is the 20th most abundant element in the Earth’s crust. It occurs in a variety of rock types and geologic environments but most often in igneous rocks in the form of zircon (ZrSiO4). Zircon is recovered as a coproduct of the mining and processing of heavy mineral sands for the titanium minerals ilmenite and rutile. The sands are formed by the weathering and erosion of rock containing zircon and titanium heavy minerals and their subsequent concentration in sedimentary systems, particularly in coastal environments. A small quantity of zirconium, less than 10 kt/a (11,000 stpy), compared with total world production of 1.4 Mt (1.5 million st) in 2012, was derived from the mineral baddeleyite (ZrO2), produced from a single source in Kovdor, Russia.

Explicit dosimetry for 2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a-mediated photodynamic therapy: macroscopic singlet oxygen modeling

PubMed Central

Penjweini, Rozhin; Liu, Baochang; Kim, Michele M.; Zhu, Timothy C.

2015-01-01

Abstract. Type II photodynamic therapy (PDT) is based on the photochemical reactions mediated through an interaction between a photosensitizer, ground-state oxygen ([O32]), and light excitation at an appropriate wavelength, which results in production of reactive singlet oxygen ([O12]rx). We use an empirical macroscopic model based on four photochemical parameters for the calculation of [O12]rx threshold concentration ([O12]rx,sh) causing tissue necrosis in tumors after PDT. For this reason, 2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a (HPPH)-mediated PDT was performed interstitially on mice with radiation-induced fibrosarcoma (RIF) tumors. A linear light source at 665 nm with total energy released per unit length of 12 to 100  J/cm and source power per unit length (LS) of 12 to 150  mW/cm was used to induce different radii of necrosis. Then the amount of [O12]rx calculated by the macroscopic model incorporating explicit PDT dosimetry of light fluence distribution, tissue optical properties, and HPPH concentration was correlated to the necrotic radius to obtain the model parameters and [O12]rx,sh. We provide evidence that [O12]rx is a better dosimetric quantity for predicting the treatment outcome than PDT dose, which is proportional to the time integral of the products of the photosensitizer concentration and light fluence rate. PMID:26720883

Oxygen partial pressure influenced structural and optical properties of DC magnetron sputtered ZrO{sub 2} films

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

Kondaiah, P.; Madhavi, V.; Uthanna, S.

2013-02-05

Thin films of zirconium oxide (ZrO{sub 2}) were deposited on (100) p-silicon and quartz substrates by sputtering of metallic zirconium target under different oxygen partial pressures in the range 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa. The effect of oxygen partial pressure on the structural and optical properties of the deposited films was systematically investigated. The deposition rate of the films decreased from 3.3 to 1.83 nm/min with the increase of oxygen partial pressure from 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa respectively. The X-ray diffraction profiles revealed that the films exhibit (111) refection of zirconium oxide in monoclinic phase.more » The optical band gap of the films increased from 5.62 to 5.80 eV and refractive index increased from 2.01 to 2.08 with the increase of oxygen partial pressure from 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa respectively.« less

Nuclear magnetic resonance analysis and activation energy spectrum of the irreversible structural relaxation of amorphous zirconium tungstate

NASA Astrophysics Data System (ADS)

Miotto, F.; Rech, G. L.; Turatti, A. M.; Catafesta, J.; Zorzi, J. E.; Pereira, A. S.; Perottoni, C. A.

2018-03-01

Zirconium tungstate undergoes a sequence of phase transitions from cubic (α -ZrW2O8 ) to orthorhombic (γ -ZrW2O8 ) to amorphous (a -ZrW2O8 ) upon increasing pressure at room temperature. The amorphous phase is known to undergo anomalous endothermic recrystallization into a high-temperature β -ZrW2O8 phase above 600∘C at ambient pressure (and back to α -ZrW2O8 when brought to room temperature). The endothermic recrystallization of a -ZrW2O8 is preceded by an irreversible exothermic structural relaxation. New W-O bonds are formed upon amorphization, continuing a tendency of increasing W coordination number in going from α to γ -ZrW2O8 . In fact, contrarily to α -ZrW2O8 , in which one-quarter of the oxygen atoms are bonded only to one W (terminal oxygens), previous works found no evidence of single-bonded oxygen atoms in a -ZrW2O8 . It thus could be argued that the irreversible character of the structural relaxation of a -ZrW2O8 is due to W-O bond breaking upon annealing of the amorphous phase. To test this hypothesis, x-ray diffraction, 17O magic-angle spinning NMR, Raman, and far-infrared analyses were performed on samples of amorphous zirconium tungstate previously annealed to increasingly higher temperatures, looking for any evidence of features that could be assigned to the presence of terminal oxygen atoms. No evidence of single-bonded oxygen was found before the onset of recrystallization. Furthermore, the kinetics of the structural relaxation of a -ZrW2O8 is consistent with a continuous spectrum of activation energy, spanning all the range from 1 to 2.5 eV . These findings suggest that the structural relaxation of amorphous zirconium tungstate, however irreversible, is not accompanied by W-O bond breaking, but most probably characterized by a succession of (mostly) irreversible local atomic rearrangements.

40 CFR 721.9973 - Zirconium dichlorides (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Zirconium dichlorides (generic). 721... Substances § 721.9973 Zirconium dichlorides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as zirconium dichlorides (PMNs P...

Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

PubMed

Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

2018-04-06

Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidized zirconium on ceramic; Catastrophic coupling.

PubMed

Ozden, V E; Saglam, N; Dikmen, G; Tozun, I R

2017-02-01

Oxidized zirconium (Oxinium™; Smith & Nephew, Memphis, TN, USA) articulated with polyethylene in total hip arthroplasty (THA) appeared to have the potential to reduce wear dramatically. The thermally oxidized metal zirconium surface is transformed into ceramic-like hard surface that is resistant to abrasion. The exposure of soft zirconium metal under hard coverage surface after the damage of oxidized zirconium femoral head has been described. It occurred following joint dislocation or in situ succeeding disengagement of polyethylene liner. We reported three cases of misuse of Oxinium™ (Smith & Nephew, Memphis, TN, USA) heads. These three cases resulted in catastrophic in situ wear and inevitable failure although there was no advice, indication or recommendation for this use from the manufacturer. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Oxygen Interaction With Space-Power Materials

NASA Technical Reports Server (NTRS)

Eck, Thomas G.; Hoffman, Richard W.

1996-01-01

Four investigations were undertaken during the period of this grant: (1 ) oxidation of molybdenum and of niobium-1 % zirconium, (2) preparation of and examination of EOIM-3 samples, (3) sputtering of Teflon by oxygen ion bombardment,and (4) sputtering of Ions from copper and aluminum by oxygen and argon ion bombardment. Investigations (1), (3), and (4) used a low-energy Ion gun to bombard surfaces within an ultra-high vacuum system. Particles ejected from the surfaces were detected by a mass spectrometer.

USSR and Eastern Europe Scientifc Abstracts Materials Science and Metallurgy No 43.

DTIC Science & Technology

1977-03-09

Institute [Abstract] A study is made of the influence of stoichiometry on the characteristics of microplastic deformation in powders of zirconium and... microplasticity , stoichiometric carbides can be arranged in the following sequence of increasing brittleness: NbC, ZrC, TiC. References 18: 13 Soviet

Zirconium behaviour during electrorefining of actinide-zirconium alloy in molten LiCl-KCl on aluminium cathodes

NASA Astrophysics Data System (ADS)

Meier, R.; Souček, P.; Malmbeck, R.; Krachler, M.; Rodrigues, A.; Claux, B.; Glatz, J.-P.; Fanghänel, Th.

2016-04-01

A pyrochemical electrorefining process for the recovery of actinides from metallic nuclear fuel based on actinide-zirconium alloys (An-Zr) in a molten salt is being investigated. In this process actinides are group-selectively recovered on solid aluminium cathodes as An-Al alloys using a LiCl-KCl eutectic melt at a temperature of 450 °C. In the present study the electrochemical behaviour of zirconium during electrorefining was investigated. The maximum amount of actinides that can be oxidised without anodic co-dissolution of zirconium was determined at a selected constant cathodic current density. The experiment consisted of three steps to assess the different stages of the electrorefining process, each of which employing a fresh aluminium cathode. The results indicate that almost a complete dissolution of the actinides without co-dissolution of zirconium is possible under the applied experimental conditions.

Separation of Zirconium and Hafnium: A Review

NASA Astrophysics Data System (ADS)

Xu, L.; Xiao, Y.; van Sandwijk, A.; Xu, Q.; Yang, Y.

Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium. This paper provides an overview of the processes for separating hafnium from zirconium. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The current dominant zirconium production route involves pyrometallurgical ore cracking, multi-step hydrometallurgical liquid-liquid extraction for hafnium removal and the reduction of zirconium tetrachloride to the pure metal by the Kroll process. The lengthy hydrometallurgical Zr-Hf separation operations leads to high production cost, intensive labour and heavy environmental burden. Using a compact pyrometallurgical separation method can simplify the whole production flowsheet with a higher process efficiency. The known separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt extraction. The commercially operating extractive distillation process is a significant advance in Zr-Hf separation technology but it suffers from high process maintenance cost. The recently developed new process based on molten salt-metal equilibrium for Zr-Hf separation shows a great potential for industrial application, which is compact for nuclear grade zirconium production starting from crude ore. In the present paper, the available separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

SEPARATING HAFNIUM FROM ZIRCONIUM

DOEpatents

Lister, B.A.J.; Duncan, J.F.

1956-08-21

A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

Oxygen sensation and social feeding mediated by a C. elegans guanylate cyclase homologue.

PubMed

Gray, Jesse M; Karow, David S; Lu, Hang; Chang, Andy J; Chang, Jennifer S; Ellis, Ronald E; Marletta, Michael A; Bargmann, Cornelia I

2004-07-15

Specialized oxygen-sensing cells in the nervous system generate rapid behavioural responses to oxygen. We show here that the nematode Caenorhabditis elegans exhibits a strong behavioural preference for 5-12% oxygen, avoiding higher and lower oxygen levels. 3',5'-cyclic guanosine monophosphate (cGMP) is a common second messenger in sensory transduction and is implicated in oxygen sensation. Avoidance of high oxygen levels by C. elegans requires the sensory cGMP-gated channel tax-2/tax-4 and a specific soluble guanylate cyclase homologue, gcy-35. The GCY-35 haem domain binds molecular oxygen, unlike the haem domains of classical nitric-oxide-regulated guanylate cyclases. GCY-35 and TAX-4 mediate oxygen sensation in four sensory neurons that control a naturally polymorphic social feeding behaviour in C. elegans. Social feeding and related behaviours occur only when oxygen exceeds C. elegans' preferred level, and require gcy-35 activity. Our results suggest that GCY-35 is regulated by molecular oxygen, and that social feeding can be a behavioural strategy for responding to hyperoxic environments.

Oxygen stabilized zirconium-vanadium-iron alloy

DOEpatents

Mendelsohn, Marshall H.; Gruen, Dieter M.

1982-01-01

An oxygen stabilized intermetallic compound having the formula (Zr.sub.1-x Ti.sub.x).sub.2-u (V.sub.1-y Fe.sub.y)O.sub.z where x=0.0 to 0.9, y=0.01 to 0.9, z=0.25 to 0.5 and u=0 to 1. The compound is capable of reversibly sorbing hydrogen at temperatures from -196.degree. C. to 200.degree. C. at pressures down to 10.sup.-6 torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices.

Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

DOE PAGES

Yu, Jianguo; Bai, Xian -Ming; El-Azab, Anter; ...

2015-03-05

In this study, oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO 2) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo (KMC) method has been used to investigate the kinetics of oxygen transport in UO 2 under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable offstoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO 2-x, oxygenmore » transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO 2+x, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that diinterstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing a explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.« less

Ternary cobalt-molybdenum-zirconium coatings for alternative energies

NASA Astrophysics Data System (ADS)

Yar-Mukhamedova, Gulmira; Ved', Maryna; Sakhnenko, Nikolay; Koziar, Maryna

2017-11-01

Consistent patterns for electrodeposition of Co-Mo-Zr coatings from polyligand citrate-pyrophosphate bath were investigated. The effect of both current density amplitude and pulse on/off time on the quality, composition and surface morphology of the galvanic alloys were determined. It was established the coating Co-Mo-Zr enrichment by molybdenum with current density increasing up to 8 A dm-2 as well as the rising of pulse time and pause duration promotes the content of molybdenum because of subsequent chemical reduction of its intermediate oxides by hydrogen ad-atoms. It was found that the content of the alloying metals in the coating Co-Mo-Zr depends on the current density and on/off times extremely and maximum Mo and Zr content corresponds to the current density interval 4-6 A dm-2, on-/off-time 2-10 ms. Chemical resistance of binary and ternary coatings based on cobalt is caused by the increased tendency to passivity and high resistance to pitting corrosion in the presence of molybdenum and zirconium, as well as the acid nature of their oxides. Binary coating with molybdenum content not less than 20 at.% and ternary ones with zirconium content in terms of corrosion deep index are in a group ;very proof;. It was shown that Co-Mo-Zr alloys exhibits the greatest level of catalytic properties as cathode material for hydrogen electrolytic production from acidic media which is not inferior a platinum electrode. The deposits Co-Mo-Zr with zirconium content 2-4 at.% demonstrate high catalytic properties in the carbon(II) oxide conversion. This confirms the efficiency of materials as catalysts for the gaseous wastes purification and gives the reason to recommend them as catalysts for red-ox processes activating by oxygen as well as electrode materials for red-ox batteries.

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammells, Anthony F.

2005-09-27

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammels, Anthony F.

2000-01-01

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

Oxygen-stabilized zirconium-vanadium-iron alloy

DOEpatents

Mendelsohn, M.H.; Gruen, D.M.

1981-06-16

An oxygen stabilized intermetallic compound is described which has the formula (Zr/sub 1-x/Ti/sub x/)/sub 2-u/(V/sub 1-y/Fe/sub y/)O/sub z/ where x = 0.0 to 0.9, y = 0.01 to 0.9, z = 0.25 to 0.5 and u = 0 to 1. The compound is capable of reversibly sorbing hydrogen at temperatures from -196/sup 0/C to 200/sup 0/C at pressures down to 10/sup -6/ torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices.

IMPROVEMENT OF THE EXTRACTION SEPARATION OF URANIUM AND ZIRCONIUM USING ZIRCONIUM-MASKING REAGENTS (in German)

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

Kyrs, M.; Caletka, R.; Selucky, P.

1963-12-01

The masking capacities of a series of reagents were studied in the zirconium extraction with tributyl phosphate solution in the presence of nitric acid. It was established that with many reagents an improvement of the separation of uranium from zirconium could be obtained. The efficiency of the reagents increases in the series tannin, oxalic acid, tiron, pyrogallol, and Arsenazo I. (tr-auth)

Production of nuclear grade zirconium: A review

NASA Astrophysics Data System (ADS)

Xu, L.; Xiao, Y.; van Sandwijk, A.; Xu, Q.; Yang, Y.

2015-11-01

Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium as a fuel cladding material. This paper provides an overview of the processes for nuclear grade zirconium production with emphasis on the methods of Zr-Hf separation. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The known pyrometallurgical Zr-Hf separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt-metal equilibrium. In the present paper, the available Zr-Hf separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

A mediator-free glucose biosensor based on glucose oxidase/chitosan/α-zirconium phosphate ternary biocomposite.

PubMed

Liu, Li-Min; Wen, Jiwu; Liu, Lijun; He, Deyong; Kuang, Ren-yun; Shi, Taqing

2014-01-15

A novel glucose oxidase/chitosan/α-zirconium phosphate (GOD/chitosan/α-ZrP) ternary biocomposite was prepared by co-intercalating glucose oxidase (GOD) and chitosan into the interlayers of α-zirconium phosphate (α-ZrP) via a delamination-reassembly procedure. The results of X-ray diffraction, infrared spectroscopy, circular dichroism, and ultraviolet spectrum characterizations indicated not only the layered and hybrid structure of the GOD/chitosan/α-ZrP ternary biocomposite but also the recovered activity of the intercalated GOD improved by the co-intercalated chitosan. By depositing the GOD/chitosan/α-ZrP biocomposite film onto a glassy carbon electrode, the direct electrochemistry of the intercalated GOD was achieved with a fast electron transfer rate constant, k(s), of 7.48±3.52 s(-1). Moreover, this GOD/chitosan/α-ZrP biocomposite modified electrode exhibited a sensitive response to glucose in the linear range of 0.25-8.0 mM (R=0.9994, n=14), with a determination limit of 0.076 mM. Copyright © 2013 Elsevier Inc. All rights reserved.

Ultrasound-mediated destruction of oxygen and paclitaxel loaded lipid microbubbles for combination therapy in hypoxic ovarian cancer cells.

PubMed

Sun, Jiangchuan; Yin, Mingyue; Zhu, Shenyin; Liu, Li; Zhu, Yi; Wang, Zhigang; Xu, Ronald X; Chang, Shufang

2016-01-01

We synthesized oxygen and paclitaxel (PTX) loaded lipid microbubbles (OPLMBs) for ultrasound mediated combination therapy in hypoxic ovarian cancer cells. Our experiments successfully demonstrated that ultrasound induced OPLMBs destruction significantly enhanced the local oxygen release. We also demonstrated that OPLMBs in combination with ultrasound (300 kHz, 0.5 W/cm(2), 15s) yielded anti-proliferative activities of 52.8 ± 2.75% and cell apoptosis ratio of 35.25 ± 0.17% in hypoxic cells at 24h after the treatment, superior to other treatment groups such as PTX only and PTX-loaded MBs (PLMBs) with or without ultrasound mediation. RT-PCR and Western blot tests further confirmed the reduced expression of HIF-1α and MDR-1/P-gp after ultrasound mediation of OPLMBs. Our experiment suggests that ultrasound mediation of oxygen and drug-loaded MBs may be a useful method to overcome chemoresistance in the hypoxic ovarian cancer cells. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

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

Xu, Dongyan, E-mail: xdy0156@sina.com; Ma, Hong; Cheng, Fei

2014-05-01

Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidicmore » property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity.« less

Quercetin as colorimetric reagent for determination of zirconium

USGS Publications Warehouse

Grimaldi, F.S.; White, C.E.

1953-01-01

Methods described in the literature for the determination of zirconium are generally designed for relatively large amounts of this element. A good procedure using colorimetric reagent for the determination of trace amounts is desirable. Quercetin has been found to yield a sensitive color reaction with zirconium suitable for the determination of from 0.1 to 50?? of zirconium dioxide. The procedure developed involves the separation of zirconium from interfering elements by precipitation with p-dimethylaminoazophenylarsonic acid prior to its estimation with quercetin. The quercetin reaction is carried out in 0.5N hydrochloric acid solution. Under the operating conditions it is indicated that quercetin forms a 2 to 1 complex with zirconium; however, a 2 to 1 and a 1 to 1 complex can coexist under special conditions. Approximate values for the equilibrium constants of the complexes are K1 = 0.33 ?? 10-5 and K2 = 1.3 ?? 10-9. Seven Bureau of Standards samples of glass sands and refractories were analyzed with excellent results. The method described should find considerable application in the analysis of minerals and other materials for macro as well as micro amounts of zirconium.

CHARACTERISTICS OF ANODIC AND CORROSION FILMS ON ZIRCONIUM

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

Misch, R.D.

1960-05-01

Zirconium anodizes similarly to tungsten in respect to the change of interference colors with applied voltage. However, the oxide layer on tungsten cannot reach as great a thickness. Hafnium does not anodize in the same way as zirconium but is similar to tantalum. By measuring the interference color and capacitative thicknesses on zirconium (Grades I and III) and a 2.5 wt.% tin ailoy, the film was found to grow less rapidly in terms of capacitance than in terms of iaterference colors. This was interpreted to mean that cracks develop in the oxide as it thickens. The effect was most pronouncedmore » on Grade III zirconium and least pronounced on the tin alloy. The reduction in capacitative thickness was especially noticeable when white oxide appeared. Comparative measurements on Grade I zirconium and 2.5 wt.% tin alloy indicated that the thickness of the oxide film on the tin alloy (after 16 hours in water) increased more rapidly with temperature than the film on zirconium. Tin is believed to act in ways to counteract the tendency of the oxide to form cracks, and to produce vacancies which promote ionic diffusion. (auth)« less

Zirconium-carbon hybrid sorbent for removal of fluoride from water: oxalic acid mediated Zr(IV) assembly and adsorption mechanism

PubMed Central

Halla, Velazquez-Jimenez Litza; Hurt Robert, H; Juan, Matos; Rene, Rangel-Mendez Jose

2014-01-01

When activated carbon (AC) is modified with zirconium(IV) by impregnation or precipitation, the fluoride adsorption capacity is typically improved. There is significant potential to improve these hybrid sorbent by controlling the impregnation conditions, which determine the assembly and dispersion of the Zr phases on carbon surfaces. Here, commercial activated carbon was modified with Zr(IV) together with oxalic acid (OA) used to maximize the zirconium dispersion and enhance fluoride adsorption. Adsorption experiments were carried out at pH 7 and 25 °C with a fluoride concentration of 40 mg L−1. The OA/Zr ratio was varied to determine the optimal conditions for subsequent fluoride adsorption. The data was analyzed using the Langmuir and Freundlich isotherm models. FTIR, XPS and the surface charge distribution were performed to elucidate the adsorption mechanism. Potentiometric titrations showed that the modified activated carbon (ZrOx-AC) possesses positive charge at pH lower than 7, and FTIR analysis demonstrated that zirconium ions interact mainly with carboxylic groups on the activated carbon surfaces. Moreover, XPS analysis demonstrated that Zr(IV) interacts with oxalate ions, and the fluoride adsorption mechanism is likely to involve –OH− exchange from zirconyl oxalate complexes. PMID:24359079

DISSOLUTION OF ZIRCONIUM-CONTAINING FUEL ELEMENTS

DOEpatents

Horn, F.L.

1961-12-12

Uranium is recovered from spent uranium fuel elements containing or clad with zirconium. These fuel elements are placed in an anhydrous solution of hydrogen fluoride and nitrogen dioxide. Within this system uranium forms a soluble complex and zirconium forms an insoluble complex. The uranium can then be separated, treated, and removed from solution as uranium hexafluoride. (AEC)

Processing fissile material mixtures containing zirconium and/or carbon

DOEpatents

Johnson, Michael Ernest; Maloney, Martin David

2013-07-02

A method of processing spent TRIZO-coated nuclear fuel may include adding fluoride to complex zirconium present in a dissolved TRIZO-coated fuel. Complexing the zirconium with fluoride may reduce or eliminate the potential for zirconium to interfere with the extraction of uranium and/or transuranics from fission materials in the spent nuclear fuel.

Nanoindentation study of bulk zirconium hydrides at elevated temperatures

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

Cinbiz, Mahmut Nedim; Balooch, Mehdi; Hu, Xunxiang

Here, the mechanical properties of zirconium hydrides was studied using nano-indentation technique at a temperature range of 25 – 400 °C. Temperature dependency of reduced elastic modulus and hardness of δ- and ε-zirconium hydrides were obtained by conducting nanoindentation experiments on the bulk hydride samples with independently heating capability of indenter and heating stage. The reduced elastic modulus of δ-zirconium hydride (H/Zr ratio =1.61) decreased from ~113 GPa to ~109 GPa while temperature increased from room temperature to 400°C. For ε-zirconium hydrides (H/Zr ratio=1.79), the reduced elastic modulus decreased from 61 GPa to 54 GPa as temperature increased from roommore » temperature to 300 °C. Whereas, hardness of δ-zirconium hydride significantly decreased from 4.1 GPa to 2.41 GPa when temperature increased from room temperature to 400 °C. Similarly, hardness of ε-zirconium hydride decreased from 3.06 GPa to 2.19 GPa with temperature increase from room temperature to 300°C.« less

Nanoindentation study of bulk zirconium hydrides at elevated temperatures

DOE PAGES

Cinbiz, Mahmut Nedim; Balooch, Mehdi; Hu, Xunxiang; ...

2017-08-02

Here, the mechanical properties of zirconium hydrides was studied using nano-indentation technique at a temperature range of 25 – 400 °C. Temperature dependency of reduced elastic modulus and hardness of δ- and ε-zirconium hydrides were obtained by conducting nanoindentation experiments on the bulk hydride samples with independently heating capability of indenter and heating stage. The reduced elastic modulus of δ-zirconium hydride (H/Zr ratio =1.61) decreased from ~113 GPa to ~109 GPa while temperature increased from room temperature to 400°C. For ε-zirconium hydrides (H/Zr ratio=1.79), the reduced elastic modulus decreased from 61 GPa to 54 GPa as temperature increased from roommore » temperature to 300 °C. Whereas, hardness of δ-zirconium hydride significantly decreased from 4.1 GPa to 2.41 GPa when temperature increased from room temperature to 400 °C. Similarly, hardness of ε-zirconium hydride decreased from 3.06 GPa to 2.19 GPa with temperature increase from room temperature to 300°C.« less

40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under this...

40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under this...

RECOVERY OF URANIUM FROM ZIRCONIUM-URANIUM NUCLEAR FUELS

DOEpatents

Gens, T.A.

1962-07-10

An improvement was made in a process of recovering uranium from a uranium-zirconium composition which was hydrochlorinated with gsseous hydrogen chloride at a temperature of from 350 to 800 deg C resulting in volatilization of the zirconium, as zirconium tetrachloride, and the formation of a uranium containing nitric acid insoluble residue. The improvement consists of reacting the nitric acid insoluble hydrochlorination residue with gaseous carbon tetrachloride at a temperature in the range 550 to 600 deg C, and thereafter recovering the resulting uranium chloride vapors. (AEC)

PROCESS OF DISSOLVING ZIRCONIUM ALLOYS

DOEpatents

Shor, R.S.; Vogler, S.

1958-01-21

A process is described for dissolving binary zirconium-uranium alloys where the uranium content is about 2%. In prior dissolution procedures for these alloys, an oxidizing agent was added to prevent the precipitation of uranium tetrafluoride. In the present method complete dissolution is accomplished without the use of the oxidizing agent by using only the stoichiometric amount or slight excess of HF required by the zirconium. The concentration of the acid may range from 2M to 10M and the dissolution is advatageously carried out at a temperature of 80 deg C.

Nanophase Nickel-Zirconium Alloys for Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram; Whitacre, jay; Valdez, Thomas

2008-01-01

Nanophase nickel-zirconium alloys have been investigated for use as electrically conductive coatings and catalyst supports in fuel cells. Heretofore, noble metals have been used because they resist corrosion in the harsh, acidic fuel cell interior environments. However, the high cost of noble metals has prompted a search for less-costly substitutes. Nickel-zirconium alloys belong to a class of base metal alloys formed from transition elements of widely different d-electron configurations. These alloys generally exhibit unique physical, chemical, and metallurgical properties that can include corrosion resistance. Inasmuch as corrosion is accelerated by free-energy differences between bulk material and grain boundaries, it was conjectured that amorphous (glassy) and nanophase forms of these alloys could offer the desired corrosion resistance. For experiments to test the conjecture, thin alloy films containing various proportions of nickel and zirconium were deposited by magnetron and radiofrequency co-sputtering of nickel and zirconium. The results of x-ray diffraction studies of the deposited films suggested that the films had a nanophase and nearly amorphous character.

Manufacturing process to reduce large grain growth in zirconium alloys

DOEpatents

Rosecrans, P.M.

1984-08-01

It is an object of the present invention to provide a procedure for desensitizing zirconium-based alloys to large grain growth (LGG) during thermal treatment above the recrystallization temperature of the alloy. It is a further object of the present invention to provide a method for treating zirconium-based alloys which have been cold-worked in the range of 2 to 8% strain to reduce large grain growth. It is another object of the present invention to provide a method for fabricating a zirconium alloy clad nuclear fuel element wherein the zirconium clad is resistant to large grain growth.

In vitro assessment of artifacts induced by titanium, titanium-zirconium and zirconium dioxide implants in cone-beam computed tomography.

PubMed

Sancho-Puchades, Manuel; Hämmerle, Christoph H F; Benic, Goran I

2015-10-01

The aim of this study was to test whether or not the intensity of artifacts around implants in cone-beam computed tomography (CBCT) differs between titanium, titanium-zirconium and zirconium dioxide implants. Twenty models of a human mandible, each containing one implant in the single-tooth gap position 45, were cast in dental stone. Five test models were produced for each of the following implant types: titanium 4.1 mm diameter (Ti4.1 ), titanium 3.3 mm diameter (Ti3.3 ), titanium-zirconium 3.3 mm diameter (TiZr3.3 ) and zirconium dioxide 3.5-4.5 mm diameter (ZrO3.5-4.5 ) implants. For control purposes, three models without implants were produced. Each model was scanned using a CBCT device. Gray values (GV) were recorded at eight circumferential positions around the implants at 0.5 mm, 1 mm and 2 mm from the implant surface (GVT est ). GV were assessed in the corresponding volumes of interest (VOI) in the control models without implants (GVC ontrol ). Differences of gray values (ΔGV) between GVT est and GVC ontrol were calculated as percentages. One-way ANOVA and post hoc tests were applied to detect differences between implant types. Mean ΔGV for ZrO3.5-4.5 presented the highest absolute values, generally followed by TiZr3.3 , Ti4.1 and Ti3.3 implants. The differences of ΔGV between ZrO3.5-4.5 and the remaining groups were statistically significant in the majority of the VOI (P ≤ 0.0167). ΔGV for TiZr3.3 , Ti4.1 and Ti3.3 implants did not differ significantly in the most VOI. For all implant types, ΔGV showed positive values buccally, mesio-buccally, lingually and disto-lingually, whereas negative values were detected mesially and distally. Zirconium dioxide implants generate significantly more artifacts as compared to titanium and titanium-zirconium implants. The intensity of artifacts around zirconium dioxide implants exhibited in average the threefold in comparison with titanium implants. © 2014 John Wiley & Sons A/S. Published by John Wiley

METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

DOEpatents

Vetrano, J.B.

1962-01-23

A method is given for preparing large, sound bodies of delta zirconium hydride. The method includes the steps of heating a zirconium body to a temperature of not less than l000 deg C, providing a hydrogen atmosphere for the zirconium body at a pressure not greater than one atmosphere, reducing the temperature slowly to 800 deg C at such a rate that cracks do not form while maintaining the hydrogen pressure substantially constant, and cooling in an atmosphere of hydrogen. (AEC)

Oxygen and indocyanine green loaded phase-transition nanoparticle-mediated photo-sonodynamic cytotoxic effects on rheumatoid arthritis fibroblast-like synoviocytes.

PubMed

Tang, Qin; Cui, Jianyu; Tian, Zhonghua; Sun, Jiangchuan; Wang, Zhigang; Chang, Shufang; Zhu, Shenyin

2017-01-01

Photodynamic therapy and sonodynamic therapy are developing, minimally invasive, and site-specific modalities for cancer therapy. A combined strategy PSDT (photodynamic therapy followed by sonodynamic therapy) has been proposed in this study. Here, we aimed to develop novel biodegradable poly(DL-lactide- co -glycolic acid) phase-transition nanoparticles simultaneously loaded with oxygen and indocyanine green (OI-NPs) and to investigate the cytotoxic effects and the potential mechanisms of OI-NP-mediated PSDT on MH7A synoviocytes. The OI-NPs were prepared using a modified double emulsion method and the physicochemical properties were determined. The cellular uptake of OI-NPs was detected by confocal microscopy and flow cytometry. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide assay, flow cytometry, and Hoechst 33342/propidium iodide double staining were used to determine the cytotoxic effect of OI-NP-mediated PSDT on MH7A cells. Fluorescence microscope and fluorescence microplate reader were used to detect reactive oxygen species (ROS) generation. The OI-NPs were a stable and efficient carrier to deliver oxygen and indocyanine green, and enhanced cellular uptake was observed in MH7A cells with the nanoparticles. OI-NP-mediated PSDT caused more serious cell damage and more evident cell apoptosis, compared with other groups. Furthermore, increased generation of intracellular ROS was detected in MH7A cells treated with PSDT. Interestingly, the OI-NP-mediated PSDT-induced cell viability loss was effectively rescued by pretreatment with the ROS scavenger N -acetylcysteine. Multifunctional OI-NPs were successfully developed and characterized for the combined delivery of oxygen and indocyanine green, and OI-NP-mediated PSDT would be a potential cytotoxic treatment for MH7A cells. This study may provide a novel strategy for the treatment of RA and develop a model of theranostic application through phase-transition nanoparticle-mediated PSDT in the future.

Oxygen and indocyanine green loaded phase-transition nanoparticle-mediated photo-sonodynamic cytotoxic effects on rheumatoid arthritis fibroblast-like synoviocytes

PubMed Central

Tang, Qin; Cui, Jianyu; Tian, Zhonghua; Sun, Jiangchuan; Wang, Zhigang; Chang, Shufang; Zhu, Shenyin

2017-01-01

Background Photodynamic therapy and sonodynamic therapy are developing, minimally invasive, and site-specific modalities for cancer therapy. A combined strategy PSDT (photodynamic therapy followed by sonodynamic therapy) has been proposed in this study. Here, we aimed to develop novel biodegradable poly(DL-lactide-co-glycolic acid) phase-transition nanoparticles simultaneously loaded with oxygen and indocyanine green (OI-NPs) and to investigate the cytotoxic effects and the potential mechanisms of OI-NP–mediated PSDT on MH7A synoviocytes. Methods The OI-NPs were prepared using a modified double emulsion method and the physicochemical properties were determined. The cellular uptake of OI-NPs was detected by confocal microscopy and flow cytometry. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide assay, flow cytometry, and Hoechst 33342/propidium iodide double staining were used to determine the cytotoxic effect of OI-NP–mediated PSDT on MH7A cells. Fluorescence microscope and fluorescence microplate reader were used to detect reactive oxygen species (ROS) generation. Results The OI-NPs were a stable and efficient carrier to deliver oxygen and indocyanine green, and enhanced cellular uptake was observed in MH7A cells with the nanoparticles. OI-NP–mediated PSDT caused more serious cell damage and more evident cell apoptosis, compared with other groups. Furthermore, increased generation of intracellular ROS was detected in MH7A cells treated with PSDT. Interestingly, the OI-NP–mediated PSDT-induced cell viability loss was effectively rescued by pretreatment with the ROS scavenger N-acetylcysteine. Conclusion Multifunctional OI-NPs were successfully developed and characterized for the combined delivery of oxygen and indocyanine green, and OI-NP–mediated PSDT would be a potential cytotoxic treatment for MH7A cells. This study may provide a novel strategy for the treatment of RA and develop a model of theranostic application through phase

Zirconium fluoride glass - Surface crystals formed by reaction with water

NASA Technical Reports Server (NTRS)

Doremus, R. H.; Bansal, N. P.; Bradner, T.; Murphy, D.

1984-01-01

The hydrated surfaces of a zirconium barium fluoride glass, which has potential for application in optical fibers and other optical elements, were observed by scanning electron microscopy. Crystalline zirconium fluoride was identified by analysis of X-ray diffraction patterns of the surface crystals and found to be the main constituent of the surface material. It was also found that hydrated zirconium fluorides form only in highly acidic fluoride solutions. It is possible that the zirconium fluoride crystals form directly on the glass surface as a result of its depletion of other ions. The solubility of zirconium fluoride is suggested to be probably much lower than that of barium fluoride (0.16 g/100 cu cm at 18 C). Dissolution was determined to be the predominant process in the initial stages of the reaction of the glass with water. Penetration of water into the glass has little effect.

Minimalistic Liquid-Assisted Route to Highly Crystalline α-Zirconium Phosphate.

PubMed

Cheng, Yu; Wang, Xiaodong Tony; Jaenicke, Stephan; Chuah, Gaik-Khuan

2017-08-24

Zirconium phosphates have potential applications in areas of ion exchange, catalysis, photochemistry, and biotechnology. However, synthesis methodologies to form crystalline α-zirconium phosphate (Zr(HPO 4 ) 2 ⋅H 2 O) typically involve the use of excess phosphoric acid, addition of HF or oxalic acid and long reflux times or hydrothermal conditions. A minimalistic sustainable route to its synthesis has been developed by using only zirconium oxychloride and concentrated phosphoric acid to form highly crystalline α-zirconium phosphate within hours. The morphology can be changed from platelets to rod-shaped particles by fluoride addition. By varying the temperature and time, α-zirconium phosphate with particle sizes from nanometers to microns can be obtained. Key features of this minimal solvent synthesis are the excellent yields obtained with high atom economy under mild conditions and ease of scalability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic modeling of α-hydrogen abstractions from unsaturated and saturated oxygenate compounds by hydrogen atoms.

PubMed

Paraskevas, Paschalis D; Sabbe, Maarten K; Reyniers, Marie-Françoise; Papayannakos, Nikos G; Marin, Guy B

2014-10-09

Hydrogen-abstraction reactions play a significant role in thermal biomass conversion processes, as well as regular gasification, pyrolysis, or combustion. In this work, a group additivity model is constructed that allows prediction of reaction rates and Arrhenius parameters of hydrogen abstractions by hydrogen atoms from alcohols, ethers, esters, peroxides, ketones, aldehydes, acids, and diketones in a broad temperature range (300-2000 K). A training set of 60 reactions was developed with rate coefficients and Arrhenius parameters calculated by the CBS-QB3 method in the high-pressure limit with tunneling corrections using Eckart tunneling coefficients. From this set of reactions, 15 group additive values were derived for the forward and the reverse reaction, 4 referring to primary and 11 to secondary contributions. The accuracy of the model is validated upon an ab initio and an experimental validation set of 19 and 21 reaction rates, respectively, showing that reaction rates can be predicted with a mean factor of deviation of 2 for the ab initio and 3 for the experimental values. Hence, this work illustrates that the developed group additive model can be reliably applied for the accurate prediction of kinetics of α-hydrogen abstractions by hydrogen atoms from a broad range of oxygenates.

DISSOLUTION OF ZIRCONIUM AND ALLOYS THEREFOR

DOEpatents

Swanson, J.L.

1961-07-11

The dissolution of zirconium cladding in a water solution of ammonium fluoride and ammonium nitrate is described. The method finds particular utility in processing spent fuel elements for nuclear reactors. The zirconium cladding is first dissolved in a water solution of ammonium fluoride and ammonium nitrate; insoluble uranium and plutonium fiuorides formed by attack of the solvent on the fuel materiai of the fuel element are then separated from the solution, and the fuel materiai is dissolved in another solution.

International strategic minerals inventory summary report; zirconium

USGS Publications Warehouse

Towner, R.R.

1992-01-01

Zircon, a zirconium silicate, is currently the most important commercial zirconium-bearing mineral. Baddeleyite, a natural form of zirconia, is less important but has some specific end uses. Both zircon and baddeleyite occur in hard-rock and placer deposits, but at present all zircon production is from placer deposits. Most baddeleyite production is from hard-rock deposits, principally as a byproduct of copper and phosphate-rock mining. World zirconium resources in identified, economically exploitable deposits are about 46 times current production rates. Of these resources, some 71 percent are in South Africa, Australia, and the United States. The principal end uses of zirconium minerals are in ceramic applications and as refractories, abrasives, and mold linings in foundries. A minor amount, mainly of zircon, is used for the production of hafnium-free zirconium metal, which is used principally for sheathing fuel elements in nuclear reactors and in the chemical-processing industry, aerospace engineering, and electronics. Australia and South Africa are the largest zircon producers and account for more than 70 percent of world output; the United States and the Soviet Union account for another 20 percent. South Africa accounts for almost all the world's production of baddeleyite, which is about 2 percent of world production of contained zirconia. Australia and South Africa are the largest exporters of zircon. Unless major new deposits are developed in countries that have not traditionally produced zircon, the pattern of world production is unlikely to change by 2020. The proportions, however, of production that come from existing producing countries may change somewhat.

PROCESS FOR DISSOLVING BINARY URANIUM-ZIRCONIUM OR ZIRCONIUM-BASE ALLOYS

DOEpatents

Jonke, A.A.; Barghusen, J.J.; Levitz, N.M.

1962-08-14

A process of dissolving uranium-- zirconium and zircaloy alloys, e.g. jackets of fuel elements, with an anhydrous hydrogen fluoride containing from 10 to 32% by weight of hydrogen chloride at between 400 and 450 deg C., preferably while in contact with a fluidized inert powder, such as calcium fluoride is described. (AEC)

Capture of Tritium Released from Cladding in the Zirconium Recycle Process

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

Spencer, Barry B.; Walker, T. B.; Bruffey, S. H.

2016-08-31

Zirconium may be recovered from the Zircaloy® cladding of used nuclear fuel (UNF) for recycle or to reduce the quantities of high-level waste destined for a geologic repository. Recovery of zirconium using a chlorination process is currently under development at the Oak Ridge National Laboratory. The approach is to treat the cladding with chlorine gas to convert the zirconium in the alloy (~98 wt % of the alloy mass) to zirconium tetrachloride. A significant fraction of the tritium (0–96%) produced in nuclear fuel during irradiation may be found in zirconium-based cladding and could be released from the cladding when themore » solid matrix is destroyed by the chlorination reaction. To prevent uncontrolled release of radioactive tritium to other parts of the plant or to the environment, a method to recover the tritium may be required. The focus of this effort was to (1) identify potential methods for the recovery of tritium from the off-gas of the zirconium recycle process, (2) perform scoping tests on selected recovery methods using nonradioactive gas simulants, and (3) select a process design appropriate for testing on radioactive gas streams generated by the engineering-scale zirconium recycle demonstrations on radioactive used cladding.« less

METHOD OF IMPROVING CORROSION RESISTANCE OF ZIRCONIUM

DOEpatents

Shannon, D.W.

1961-03-28

An improved intermediate rinse for zirconium counteracts an anomalous deposit that often results in crevices and outof-the-way places when ordinary water is used to rinse away a strong fluoride etching solution designed to promote passivation of the metal. The intermediate rinse, which is used after the etching solution and before the water, is characterized by a complexing agent for fluoride ions such as aluminum or zirconium nitrates or chlorides.

40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants to waters of the...

Zirconium determination by cooling curve analysis during the pyroprocessing of used nuclear fuel

NASA Astrophysics Data System (ADS)

Westphal, B. R.; Price, J. C.; Bateman, K. J.; Marsden, K. C.

2015-02-01

An alternative method to sampling and chemical analyses has been developed to monitor the concentration of zirconium in real-time during the casting of uranium products from the pyroprocessing of used nuclear fuel. The method utilizes the solidification characteristics of the uranium products to determine zirconium levels based on standard cooling curve analyses and established binary phase diagram data. Numerous uranium products have been analyzed for their zirconium content and compared against measured zirconium data. From this data, the following equation was derived for the zirconium content of uranium products:

Direct synthesis of zirconium powder by magnesium reduction

NASA Astrophysics Data System (ADS)

Lee, Dong-Won; Yun, Jung-Yeul; Yoon, Sung-Won; Wang, Jei-Pil

2013-05-01

The direct synthesis of zirconium powder has been conducted through an analysis of the chemical reaction between evaporated ZrCl4 and molten magnesium over a range of reduction temperatures, concentration of hydrochloric acid, and stirring time. The observed results indicated that the purity of zirconium powder increased with increased stirring time, and Mg and MgCl2 were removed by 10 wt% of hydrochloric acid solution. The pure zirconium powder was obtained by stirring again for 5 h using 5 wt% of hydrochloric acid solution. It was noted that the mean particle size increased when the reaction temperature was increased, and the size of the powder at 1,123 K and 1,173 K was found to be 10 μm and 15 μm, respectively. In addition, the purity of the powder was also improved with temperature, and its purity finally reached up to 99.5% at 1,250 K. Overall, pure zirconium powder was obtained after a stirring stage for 5 hours using 5 wt% of hydrochloric acid solution.

Nuclear-grade zirconium prepared by combining combustion synthesis with molten-salt electrorefining technique

NASA Astrophysics Data System (ADS)

Li, Hui; Nersisyan, Hayk H.; Park, Kyung-Tae; Park, Sung-Bin; Kim, Jeong-Guk; Lee, Jeong-Min; Lee, Jong-Hyeon

2011-06-01

Zirconium has a low absorption cross-section for neutrons, which makes it an ideal material for use in nuclear reactor applications. However, hafnium typically contained in zirconium causes it to be far less useful for nuclear reactor materials because of its high neutron-absorbing properties. In the present study, a novel effective method has been developed for the production of hafnium-free zirconium. The process includes two main stages: magnesio-thermic reduction of ZrSiO 4 under a combustion mode, to produce zirconium silicide (ZrSi), and recovery of hafnium-free zirconium by molten-salt electrorefining. It was found that, depending on the electrorefining procedure, it is possible to produce zirconium powder with a low hafnium content: 70 ppm, determined by ICP-AES analysis.

Capture of Tritium Released from Cladding in the Zirconium Recycle Process

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

Spencer, Barry B.; Walker, T. B.; Bruffey, Stephanie H.

2016-08-31

This report is issued as the first revision to FCRD-MRWFD-2016-000297. Zirconium may be recovered from the Zircaloy® cladding of used nuclear fuel (UNF) for recycle or to reduce the quantities of high-level waste destined for a geologic repository. Recovery of zirconium using a chlorination process is currently under development at the Oak Ridge National Laboratory. The approach is to treat the cladding with chlorine gas to convert the zirconium in the alloy (~98 wt % of the alloy mass) to zirconium tetrachloride. A significant fraction of the tritium (0–96%) produced in nuclear fuel during irradiation may be found in zirconium-basedmore » cladding and could be released from the cladding when the solid matrix is destroyed by the chlorination reaction. To prevent uncontrolled release of radioactive tritium to other parts of the plant or to the environment, a method to recover the tritium may be required. The focus of this effort was to (1) identify potential methods for the recovery of tritium from the off-gas of the zirconium recycle process, (2) perform scoping tests on selected recovery methods using non-radioactive gas simulants, and (3) select a process design appropriate for testing on radioactive gas streams generated by the engineering-scale zirconium recycle demonstrations on radioactive used cladding.« less

40 CFR 721.10598 - Lead strontium titanium zirconium oxide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lead strontium titanium zirconium... Specific Chemical Substances § 721.10598 Lead strontium titanium zirconium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as lead strontium...

40 CFR 721.10598 - Lead strontium titanium zirconium oxide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Lead strontium titanium zirconium... Specific Chemical Substances § 721.10598 Lead strontium titanium zirconium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as lead strontium...

Regio- and Stereospecific Formation of Protected Allylic Alcohols via Zirconium-Mediated SN2' Substitution of Allylic Chlorides

PubMed Central

Fox, Richard J.; Lalic, Gojko; Bergman, Robert G.

2008-01-01

A new, highly regio- and stereospecific SN2' substitution reaction between a zirconium oxo complex and allylic chloride has been achieved. The resulting allylic alcohol or TBS-protected allylic ether products were isolated in good to excellent yields with a wide range of E-allylic chlorides. A mechanism for the SN2' allylic substitution consistent with kinetic, stereochemical and secondary isotope effect studies was proposed. PMID:17973391

Fluorometric determination of zirconium in minerals

USGS Publications Warehouse

Alford, W.C.; Shapiro, L.; White, C.E.

1951-01-01

The increasing use of zirconium in alloys and in the ceramics industry has created renewed interest in methods for its determination. It is a common constituent of many minerals, but is usually present in very small amounts. Published methods tend to be tedious, time-consuming, and uncertain as to accuracy. A new fluorometric procedure, which overcomes these objections to a large extent, is based on the blue fluorescence given by zirconium and flavonol in sulfuric acid solution. Hafnium is the only element that interferes. The sample is fused with borax glass and sodium carbonate and extracted with water. The residue is dissolved in sulfuric acid, made alkaline with sodium hydroxide to separate aluminum, and filtered. The precipitate is dissolved in sulfuric acid and electrolysed in a Melaven cell to remove iron. Flavonol is then added and the fluorescence intensity is measured with a photo-fluorometer. Analysis of seven standard mineral samples shows excellent results. The method is especially useful for minerals containing less than 0.25% zirconium oxide.

Langley 8-foot high-temperature tunnel oxygen measurement system

NASA Technical Reports Server (NTRS)

Sprinkle, Danny R.; Chen, Tony D.; Chaturvedi, Sushil K.

1991-01-01

In order to ensure that there is a proper amount of oxygen necessary for sustaining test engine operation for hypersonic propulsion systems testing at the NASA Langley 8-foot high-temperature tunnel, a quickly responding real-time measurement system of test section oxygen concentration has been designed and tested at Langley. It is built around a zirconium oxide-based sensor which develops a voltage proportional to the oxygen partial pressure of the test gas. The voltage signal is used to control the amount of oxygen being injected into the combustor air. The physical operation of the oxygen sensor is described, as well as the sampling system used to extract the test gas from the tunnel test section. Results of laboratory tests conducted to verify sensor accuracy and response time performance are discussed, as well as the final configuration of the system to be installed in the tunnel.

Electrical insulator assembly with oxygen permeation barrier

DOEpatents

Van Der Beck, R.R.; Bond, J.A.

1994-03-29

A high-voltage electrical insulator for electrically insulating a thermoelectric module in a spacecraft from a niobium-1% zirconium alloy wall of a heat exchanger filled with liquid lithium while providing good thermal conductivity between the heat exchanger and the thermoelectric module. The insulator has a single crystal alumina layer (SxAl[sub 2]O[sub 3], sapphire) with a niobium foil layer bonded thereto on the surface of the alumina crystal facing the heat exchanger wall, and a molybdenum layer bonded to the niobium layer to act as an oxygen permeation barrier to preclude the oxygen depleting effects of the lithium from causing undesirable niobium-aluminum intermetallic layers near the alumina-niobium interface. 3 figures.

NEUTRON REACTOR FUEL ELEMENT UTILIZING ZIRCONIUM-BASE ALLOYS

DOEpatents

Saller, H.A.; Keeler, J.R.; Szumachowski, E.R.

1957-11-12

This patent relates to clad fuel elements for use in neutronic reactors and is drawn to such a fuel element which consists of a core of fissionable material, comprised of an alloy of zirconium and U/sup 235/ enriched uranium, encased in a jacket of a binary zirconium-tin alloy in which the tin content ranges between 1 and 15% by weight.

Geologic structure of Gofitsky deposit of titanium and zirconium and perspectives of the reserve base of titanium and zirconium in Russia

NASA Astrophysics Data System (ADS)

Kukhmazov, Iskander

2016-04-01

With the fall of the Soviet Union, all the mining deposits of titanium and zirconium appeared outside of Russian Federation. Therefore the studying of deposits of titanium and zirconium in Russia is very important nowadays. There is a paradoxical situation in the country: in spite of possible existence of national mineral resource base of Ti-Zr material, which can cover needs of the country, Russia is the one of the largest buyers of imported Ti-Zr material in the world. Many deposits are not mined, and those which are in the process of mining have poor reserves. Demand for this raw material is very great not only for Russia, but also for the world in general. Today there is a scarcity of zircon around the world and it will only increase through time. Therefore prices of products of titanium and zirconium also increase. Consequently Russian deposits of titanium and zirconium with higher content than foreign may become competitive. Russia is forced to buy raw materials (zirconium and titanium production) from former Soviet Union countries at prices higher than the world's and thus incur huge losses, including customs charges. Russia should create its own mineral resource base of Ti-Zr. Studied titanium-zirconium deposits of Stavropol region may become the basis for the south part of Russia. At first, Beshpagirsky deposit should be pointed out. It has large reserves of ore sands with high content of Ti-Zr. A combination of favorable geographical position of the area with developed industrial infrastructure makes it very beneficial as an object for high priority development. Gofitsky deposit should be pointed out as well. Its sands have a wide areal distribution and a high content of titanium and zirconium. Chokrak, Karagan-Konksk and Sarmatian sediments of the Miocene of Gofitsky deposit are productive for titanium and zirconium placers within Stavropol region of Russia. Gofitsky deposit was evaluated from financial and economic point of view and the following data

METHOD OF PREPARING SINTERED ZIRCONIUM METAL FROM ITS HYDRIDES

DOEpatents

Angier, R.P.

1958-02-11

The invention relates to the preparation of metal shapes from zirconium hydride by powder metallurgical techniques. The zirconium hydride powder which is to be used for this purpose can be prepared by rendering massive pieces of crystal bar zirconium friable by heat treatment in purified hydrogen. This any then be ground into powder and powder can be handled in the air without danger of it igniting. It may then be compacted in the normal manner by being piaced in a die. The compact is sintered under vacuum conditions preferably at a temperature ranging from 1200 to 1300 deg C and for periods of one to three hours.

Skeletal muscle microvascular oxygenation dynamics in heart failure: exercise training and nitric oxide-mediated function.

PubMed

Hirai, Daniel M; Copp, Steven W; Holdsworth, Clark T; Ferguson, Scott K; McCullough, Danielle J; Behnke, Bradley J; Musch, Timothy I; Poole, David C

2014-03-01

Chronic heart failure (CHF) impairs nitric oxide (NO)-mediated regulation of skeletal muscle O2 delivery-utilization matching such that microvascular oxygenation falls faster (i.e., speeds PO2mv kinetics) during increases in metabolic demand. Conversely, exercise training improves (slows) muscle PO2mv kinetics following contractions onset in healthy young individuals via NO-dependent mechanisms. We tested the hypothesis that exercise training would improve contracting muscle microvascular oxygenation in CHF rats partly via improved NO-mediated function. CHF rats (left ventricular end-diastolic pressure = 17 ± 2 mmHg) were assigned to sedentary (n = 11) or progressive treadmill exercise training (n = 11; 5 days/wk, 6-8 wk, final workload of 60 min/day at 35 m/min; -14% grade downhill running) groups. PO2mv was measured via phosphorescence quenching in the spinotrapezius muscle at rest and during 1-Hz twitch contractions under control (Krebs-Henseleit solution), sodium nitroprusside (SNP; NO donor; 300 μM), and N(G)-nitro-l-arginine methyl ester (L-NAME, nonspecific NO synthase blockade; 1.5 mM) superfusion conditions. Exercise-trained CHF rats had greater peak oxygen uptake and spinotrapezius muscle citrate synthase activity than their sedentary counterparts (p < 0.05 for both). The overall speed of the PO2mv fall during contractions (mean response time; MRT) was slowed markedly in trained compared with sedentary CHF rats (sedentary: 20.8 ± 1.4, trained: 32.3 ± 3.0 s; p < 0.05), and the effect was not abolished by L-NAME (sedentary: 16.8 ± 1.5, trained: 31.0 ± 3.4 s; p > 0.05). Relative to control, SNP increased MRT in both groups such that trained CHF rats had slower kinetics (sedentary: 43.0 ± 6.8, trained: 55.5 ± 7.8 s; p < 0.05). Improved NO-mediated function is not obligatory for training-induced improvements in skeletal muscle microvascular oxygenation (slowed PO2mv kinetics) following contractions onset in rats with CHF.

Skeletal muscle microvascular oxygenation dynamics in heart failure: exercise training and nitric oxide-mediated function

PubMed Central

Copp, Steven W.; Holdsworth, Clark T.; Ferguson, Scott K.; McCullough, Danielle J.; Behnke, Bradley J.; Musch, Timothy I.; Poole, David C.

2014-01-01

Chronic heart failure (CHF) impairs nitric oxide (NO)-mediated regulation of skeletal muscle O2 delivery-utilization matching such that microvascular oxygenation falls faster (i.e., speeds PO2mv kinetics) during increases in metabolic demand. Conversely, exercise training improves (slows) muscle PO2mv kinetics following contractions onset in healthy young individuals via NO-dependent mechanisms. We tested the hypothesis that exercise training would improve contracting muscle microvascular oxygenation in CHF rats partly via improved NO-mediated function. CHF rats (left ventricular end-diastolic pressure = 17 ± 2 mmHg) were assigned to sedentary (n = 11) or progressive treadmill exercise training (n = 11; 5 days/wk, 6–8 wk, final workload of 60 min/day at 35 m/min; −14% grade downhill running) groups. PO2mv was measured via phosphorescence quenching in the spinotrapezius muscle at rest and during 1-Hz twitch contractions under control (Krebs-Henseleit solution), sodium nitroprusside (SNP; NO donor; 300 μM), and NG-nitro-l-arginine methyl ester (L-NAME, nonspecific NO synthase blockade; 1.5 mM) superfusion conditions. Exercise-trained CHF rats had greater peak oxygen uptake and spinotrapezius muscle citrate synthase activity than their sedentary counterparts (p < 0.05 for both). The overall speed of the PO2mv fall during contractions (mean response time; MRT) was slowed markedly in trained compared with sedentary CHF rats (sedentary: 20.8 ± 1.4, trained: 32.3 ± 3.0 s; p < 0.05), and the effect was not abolished by L-NAME (sedentary: 16.8 ± 1.5, trained: 31.0 ± 3.4 s; p > 0.05). Relative to control, SNP increased MRT in both groups such that trained CHF rats had slower kinetics (sedentary: 43.0 ± 6.8, trained: 55.5 ± 7.8 s; p < 0.05). Improved NO-mediated function is not obligatory for training-induced improvements in skeletal muscle microvascular oxygenation (slowed PO2mv kinetics) following contractions onset in rats with CHF. PMID:24414070

Mechanical resistance of zirconium implant abutments: A review of the literature

PubMed Central

Vaquero-Aguilar, Cristina; Torres-Lagares, Daniel; Jiménez-Melendo, Manuel; Gutiérrez-Pérez, José L.

2012-01-01

The increase of aesthetic demands, together with the successful outcome of current implants, has renewed interest in the search for new materials with enough mechanical properties and better aesthetic qualities than the materials customarily used in implanto-prosthetic rehabilitation. Among these materials, zirconium has been used in different types of implants, including prosthetic abutments. The aim of the present review is to analyse current scientific evidence supporting the use of this material for the above mentioned purposes. We carried out the review of the literature published in the last ten years (2000 through 2010) of in vitro trials of dynamic and static loading of zirconium abutments found in the databases of Medline and Cochrane using the key words zirconium abutment, fracture resistance, fracture strength, cyclic loading. Although we have found a wide variability of values among the different studies, abutments show favourable clinical behaviour for the rehabilitation of single implants in the anterior area. Such variability may be explained by the difficulty to simulate daily mastication under in vitro conditions. The clinical evidence, as found in our study, does not recommend the use of implanto-prosthetic zirconium abutments in the molar area. Key words: Zirconium abutment, zirconium implant abutment, zirconia abutment, fracture resistance, fracture strength, cyclic loading. PMID:22143702

40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the primary zirconium and hafnium subcategory. The provisions of this subpart are applicable to discharges resulting...

Physical characterization of a new composition of oxidized zirconium-2.5 wt% niobium produced using a two step process for biomedical applications

NASA Astrophysics Data System (ADS)

Pawar, V.; Weaver, C.; Jani, S.

2011-05-01

Zirconium and particularly Zr-2.5 wt%Nb (Zr2.5Nb) alloy are useful for engineering bearing applications because they can be oxidized in air to form a hard surface ceramic. Oxidized zirconium (OxZr) due to its abrasion resistant ceramic surface and biocompatible substrate alloy has been used as a bearing surface in total joint arthroplasty for several years. OxZr is characterized by hard zirconium oxide (oxide) formed on Zr2.5Nb using one step thermal oxidation carried out in air. Because the oxide is only at the surface, the bulk material behaves like a metal, with high toughness. The oxide, furthermore, exhibits high adhesion to the substrate because of an oxygen-rich diffusion hardened zone (DHZ) interposing between the oxide and the substrate. In this study, we demonstrate a two step process that forms a thicker DHZ and thus increased depth of hardening than that can be obtained using a one step oxidation process. The first step is thermal oxidation in air and the second step is a heat treatment in vacuum. The second step drives oxygen from the oxide formed in the first step deeper into the substrate to form a thicker DHZ. During the process only a portion of the oxide is dissolved. This new composition (DHOxZr) has approximately 4-6 μm oxide similar to that of OxZr. The nano-hardness of the oxide is similar but the DHZ is approximately 10 times thicker. The stoichiometry of the oxide is similar and a secondary phase rich in oxygen is present through the entire thickness. Due to the increased depth of hardening, the critical load required for the onset of oxide cracking is approximately 1.6 times more than that of the oxide of OxZr. This new composition has a potential to be used as a bearing surface in applications where greater depth of hardening is required.

Thermochemistry of amorphous and crystalline zirconium and hafnium silicates.

NASA Astrophysics Data System (ADS)

Ushakov, S.; Brown, C. E.; Navrotsky, Alexandra; Boatner, L. A.; Demkov, A. A.; Wang, C.; Nguyen, B.-Y.

2003-03-01

Calorimetric investigation of amorphous and crystalline zirconium and hafnium silicates was performed as part of a research program on thermochemistry of alternative gate dielectrics. Amorphous hafnium and zirconium silicates with varying SiO2 content were synthesized by a sol-gel process. Crystalline zirconium and hafnium silicates (zircon and hafnon) were synthesized by solid state reaction at 1450 °C from amorphous gels and grown as single crystals from flux. High temperature oxide melt solution calorimetry in lead borate (2PbO.B2O3) solvent at 800 oC was used to measure drop solution enthalpies for amorphous and crystalline zirconium and hafnium silicates and corresponding oxides. Applying appropriate thermochemical cycles, formation enthalpy of crystalline ZrSiO4 (zircon) from binary oxides (baddeleite and quartz) at 298 K was calculated as -23 +/-2 kJ/mol and enthalpy difference between amorphous and crystalline zirconium silicate (vitrification enthalpy) was found to be 61 +/-3 kJ/mol. Crystallization onset temperatures of amorphous zirconium and hafnium silicates, as measured by differential scanning calorimetry (DSC), increased with silica content. The resulting crystalline phases, as characterized by X-ray diffraction (XRD), were tetragonal HfO2 and ZrO2. Critical crystallite size for tetragonal to monoclinic transformation of HfO2 in the gel was estimated as 6 +/-2 nm from XRD data Crystallization enthalpies per mole of hafnia and zirconia in gels decrease slightly together with crystallite size with increasing silica content, for example from -22 to -15 +/-1 kJ per mol of HfO2 crystallized at 740 and 1006 °C from silicates with 10 and 70 mol Applications of thermal analyses and solution calorimetry techniques together with first-principles density functional calculations to estimate interface and surface energies are discussed.

[The clinical application of zirconium-dioxide-ceramics. Case report].

PubMed

Somfai, Dóra; Zsigmond, Ágnes; Károlyházy, Katalin; Kispély, Barbara; Hermann, Péter

2015-12-01

Due to its outstanding physical, mechanical and esthetic properties, zirconium-dioxide is one of the most popular non-metal denture, capable of surpassing PFM in most cases. The recent advances of CAD/CAM technology makes it a good alternitve. Here we show the usefulness of zirconium-dioxide in everyday dental practice through three case reports.

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

DOE PAGES

Zheng, Tao; Yang, Zaixing; Gui, Daxiang; ...

2017-05-30

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. We overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. Furthermore, these compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest voidmore » volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.« less

Comparison of Zirconium Phosphonate-Modified Surfaces for Immobilizing Phosphopeptides and Phosphate-Tagged Proteins.

PubMed

Forato, Florian; Liu, Hao; Benoit, Roland; Fayon, Franck; Charlier, Cathy; Fateh, Amina; Defontaine, Alain; Tellier, Charles; Talham, Daniel R; Queffélec, Clémence; Bujoli, Bruno

2016-06-07

Different routes for preparing zirconium phosphonate-modified surfaces for immobilizing biomolecular probes are compared. Two chemical-modification approaches were explored to form self-assembled monolayers on commercially available primary amine-functionalized slides, and the resulting surfaces were compared to well-characterized zirconium phosphonate monolayer-modified supports prepared using Langmuir-Blodgett methods. When using POCl3 as the amine phosphorylating agent followed by treatment with zirconyl chloride, the result was not a zirconium-phosphonate monolayer, as commonly assumed in the literature, but rather the process gives adsorbed zirconium oxide/hydroxide species and to a lower extent adsorbed zirconium phosphate and/or phosphonate. Reactions giving rise to these products were modeled in homogeneous-phase studies. Nevertheless, each of the three modified surfaces effectively immobilized phosphopeptides and phosphopeptide tags fused to an affinity protein. Unexpectedly, the zirconium oxide/hydroxide modified surface, formed by treating the amine-coated slides with POCl3/Zr(4+), afforded better immobilization of the peptides and proteins and efficient capture of their targets.

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

PubMed Central

Zheng, Tao; Yang, Zaixing; Gui, Daxiang; Liu, Zhiyong; Wang, Xiangxiang; Dai, Xing; Liu, Shengtang; Zhang, Linjuan; Gao, Yang; Chen, Lanhua; Sheng, Daopeng; Wang, Yanlong; Diwu, Juan; Wang, Jianqiang; Zhou, Ruhong; Chai, Zhifang; Albrecht-Schmitt, Thomas E.; Wang, Shuao

2017-01-01

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. Herein, we overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. These compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest void volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism. PMID:28555656

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

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

Zheng, Tao; Yang, Zaixing; Gui, Daxiang

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. We overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. Furthermore, these compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest voidmore » volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.« less

Zirconium diselenite microstructures, formation and mechanism

NASA Astrophysics Data System (ADS)

Naik, Chandan C.; Salker, A. V.

2018-04-01

In this work, a series of microstructures of zirconium diselenite (Zr(SeO3)2) has been prepared via a simple precipitation method at room temperature without adding any organic surfactants. Phase purity of the sample has been checked by X-ray Diffraction. From the SEM, FESEM, and TEM images spheroid nanoparticles to the starfish-like structure of zirconium diselenite are detected. The morphological evolution processes were investigated carefully following time-dependent experiments and a growth mechanism has been proposed. Two different crystal growth processes, the oriented attachment process accompanying the Ostwald ripening process were held responsible for the formation of a structure resembling starfish having four arms.

Process for electroless deposition of metals on zirconium materials

DOEpatents

Donaghy, Robert E.

1978-01-01

A process for the electroless deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electroless plating solution containing the metal to be deposited on the article upon sufficient contact with the article.

Process for electrolytic deposition of metals on zirconium materials

DOEpatents

Donaghy, Robert E.

1979-01-30

A process for the electrolytic deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electrolytic plating solution containing the metal to be deposited on the article in the presence of an electrode receiving current.

Menadione induces the formation of reactive oxygen species and depletion of GSH-mediated apoptosis and inhibits the FAK-mediated cell invasion.

PubMed

Kim, Yun Jeong; Shin, Yong Kyoo; Sohn, Dong Suep; Lee, Chung Soo

2014-09-01

Menadione induces apoptosis in tumor cells. However, the mechanism of apoptosis in ovarian cancer cells exposed to menadione is not clear. In addition, it is unclear whether menadione-induced apoptosis is mediated by the depletion of glutathione (GSH) contents that is associated with the formation of reactive oxygen species. Furthermore, the effect of menadione on the invasion and migration of human epithelial ovarian cancer cells has not been studied. Therefore, we investigated the effects of menadione exposure on apoptosis, cell adhesion, and cell migration using the human epithelial ovarian carcinoma cell lines OVCAR-3 and SK-OV-3. The results suggest that menadione may induce apoptotic cell death in ovarian carcinoma cell lines by activating the mitochondrial pathway and the caspase-8- and Bid-dependent pathways. The apoptotic effect of menadione appears to be mediated by the formation of reactive oxygen species and the depletion of GSH. Menadione inhibited fetal-bovine-serum-induced cell adhesion and migration of OVCAR-3 cells, possibly through the suppression the focal adhesion kinase (FAK)-dependent activation of cytoskeletal-associated components. Therefore, menadione might be beneficial in the treatment of epithelial ovarian adenocarcinoma and combination therapy.

40 CFR 721.10602 - Lead niobium titanium zirconium oxide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... as specified in § 721.90 (a)(4), (b)(4), and (c)(4) (Where N=8, and 8 is an aggregate of releases for the following substances: Lead strontium titanium zirconium oxide (PMN P-11-270; CAS No. 61461-40-3... strontium titanium tungsten oxide (PMN P-11-272; CAS No. 1262279-30-0); Lanthanum lead titanium zirconium...

40 CFR 721.10602 - Lead niobium titanium zirconium oxide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... as specified in § 721.90 (a)(4), (b)(4), and (c)(4) (Where N=8, and 8 is an aggregate of releases for the following substances: Lead strontium titanium zirconium oxide (PMN P-11-270; CAS No. 61461-40-3... strontium titanium tungsten oxide (PMN P-11-272; CAS No. 1262279-30-0); Lanthanum lead titanium zirconium...

Surface characterization of anodized zirconium for biomedical applications

NASA Astrophysics Data System (ADS)

Sanchez, A. Gomez; Schreiner, W.; Duffó, G.; Ceré, S.

2011-05-01

Mechanical properties and corrosion resistance of zirconium make this material suitable for biomedical implants. Its good in vivo performance is mainly due to the presence of a protective oxide layer that minimizes corrosion rate, diminishes the amount of metallic ions released to the biological media and facilitates the osseointegration process. Since the implant surface is the region in contact with living tissues, the characteristics of the surface film are of great interest. Surface modification is a route to enhance both biocompatibility and corrosion resistance of permanent implant materials. Anodizing is presented as an interesting process to modify metal surfaces with good reproducibility and independence of the geometry. In this work the surface of zirconium before and after anodizing in 1 mol/L phosphoric acid solution at a fixed potential between 3 and 30 V, was characterized by means of several surface techniques. It was found that during anodization the surface oxide grows with an inhomogeneous coverage on zirconium surface, modifying the topography. The incorporation of P from the electrolyte to the surface oxide during the anodizing process changes the surface chemistry. After 30 days of immersion in Simulated Body Fluid (SBF) solution, Ca-P rich compounds were present on anodized zirconium.

The Deformation Mechanism of Fatigue Behaviour in a N36 Zirconium Alloy

NASA Astrophysics Data System (ADS)

Wang, Yingzhu

2018-05-01

Zirconium alloys are widely used as claddings in nuclear reactor. A N36 zirconium alloy has been deformed into a sheet with highly texture according to the result of electron back scatter diffraction test. Then this N36 zirconium alloy sheet has been cut into small beam samples with 12 x 3 x 3 mm3 in size. In this experiment, a three-point bending test was carried out to investigate the fatigue behaviour of N36 zirconium alloy. Cyclic loadings were applied on the top middle of the beam samples. The region of interest (ROI) is located at the middle bottom of the front face of the beam sample where slip band was observed in deformed beam sample due to strain concentration by using scanning electron microscopy. Twinning also plays an important role to accommodate the plastic deformation of N36 zirconium alloy in fatigue, which displays competition with slip.

Electrical insulator assembly with oxygen permeation barrier

DOEpatents

Van Der Beck, Roland R.; Bond, James A.

1994-01-01

A high-voltage electrical insulator (21) for electrically insulating a thermoelectric module (17) in a spacecraft from a niobium-1% zirconium alloy wall (11) of a heat exchanger (13) filled with liquid lithium (16) while providing good thermal conductivity between the heat exchanger and the thermoelectric module. The insulator (21) has a single crystal alumina layer (SxAl.sub.2 O.sub.3, sapphire) with a niobium foil layer (32) bonded thereto on the surface of the alumina crystal (26) facing the heat exchanger wall (11), and a molybdenum layer (31) bonded to the niobium layer (32) to act as an oxygen permeation barrier to preclude the oxygen depleting effects of the lithium from causing undesirable niobium-aluminum intermetallic layers near the alumina-niobium interface.

SEPARATION OF URANIUM FROM ZIRCONIUM AND NIOBIUM BY SOLVENT EXTRACTION

DOEpatents

Voiland, E.E.

1958-05-01

A process for separation of the uranium from zirconium and/or niobium values contained in 3 to 7M aqueous nitric acid solutions is described. This is accomplished by adding phosphoric acid anions to the nitric acid solution containing the uranium, zirconium, and/or niobium in an amount sufficient to make the solution 0.05 to 0.2M in phosphate ion and contacting the solution with an organic water-immiscible solvent such as MEK, whereby the uranyl values are taken up by the extract phase while the zirconium and niobium preferentially remain in the aqueous raffinate.

In-situ stabilization of radioactive zirconium swarf

DOEpatents

Hess, Clay C.

1999-01-01

The method for treating ignitable cutting swarf in accordance with the present invention involves collecting cutting swarf in a casting mold underwater and injecting a binder mixture comprising vinyl ester styrene into the vessel to fill void volume; and form a mixture comprising swarf and vinyl ester styrene; and curing the mixture. The method is especially useful for stabilizing the ignitable characteristics of radioactive zirconium cutting swarf, and can be used to solidify zirconium swarf, or other ignitable finely divided material, underwater. The process could also be performed out of water with other particulate wastes.

Oxygen-conserving reflexes of the brain: the current molecular knowledge

PubMed Central

Schaller, B; Cornelius, J F; Sandu, N; Ottaviani, G; Perez-Pinzon, M A

2009-01-01

Abstract The trigemino-cardiac reflex (TCR) may be classified as a sub-phenomenon in the group of the so-called ‘oxygen-conserving reflexes’. Within seconds after the initiation of such a reflex, there is neither a powerful and differentiated activation of the sympathetic system with subsequent elevation in regional cerebral blood flow (CBF) with no changes in the cerebral metabolic rate of oxygen (CMRO2) or in the cerebral metabolic rate of glucose (CMRglc). Such an increase in regional CBF without a change of CMRO2 or CMRglc provides the brain with oxygen rapidly and efficiently and gives substantial evidence that the TCR is an oxygen-conserving reflex. This system, which mediates reflex protection projects via currently undefined pathways from the rostral ventrolateral medulla oblongata to the upper brainstem and/or thalamus which finally engage a small population of neurons in the cortex. This cortical centre appears to be dedicated to reflexively transduce a neuronal signal into cerebral vasodilatation and synchronization of electrocortical activity. Sympathetic excitation is mediated by cortical-spinal projection to spinal pre-ganglionic sympathetic neurons whereas bradycardia is mediated via projections to cardiovagal motor medullary neurons. The integrated reflex response serves to redistribute blood from viscera to brain in response to a challenge to cerebral metabolism, but seems also to initiate a preconditioning mechanism. Better and more detailed knowledge of the cascades, transmitters and molecules engaged in such endogenous (neuro) protection may provide new insights into novel therapeutic options for a range of disorders characterized by neuronal death and into cortical organization of the brain. PMID:19438971

Identifying the Nonradical Mechanism in the Peroxymonosulfate Activation Process: Singlet Oxygenation Versus Mediated Electron Transfer.

PubMed

Yun, Eun-Tae; Lee, Jeong Hoon; Kim, Jaesung; Park, Hee-Deung; Lee, Jaesang

2018-06-01

Select persulfate activation processes were demonstrated to initiate oxidation not reliant on sulfate radicals, although the underlying mechanism has yet to be identified. This study explored singlet oxygenation and mediated electron transfer as plausible nonradical mechanisms for organic degradation by carbon nanotube (CNT)-activated peroxymonosulfate (PMS). The degradation of furfuryl alcohol (FFA) as a singlet oxygen ( 1 O 2 ) indicator and the kinetic retardation of FFA oxidation in the presence of l-histidine and azide as 1 O 2 quenchers apparently supported a role of 1 O 2 in the CNT/PMS system. However, the 1 O 2 scavenging effect was ascribed to a rapid PMS depletion by l-histidine and azide. A comparison of CNT/PMS and photoexcited Rose Bengal (RB) excluded the possibility of singlet oxygenation during heterogeneous persulfate activation. In contrast to the case of excited RB, solvent exchange (H 2 O to D 2 O) did not enhance FFA degradation by CNT/PMS and the pH- and substrate-dependent reactivity of CNT/PMS did not reflect the selective nature of 1 O 2 . Alternatively, concomitant PMS reduction and trichlorophenol oxidation were achieved when PMS and trichlorophenol were physically separated in two chambers using a conductive vertically aligned CNT membrane. This result suggested that CNT-mediated electron transfer from organics to persulfate was primarily responsible for the nonradical degradative route.

Concept Feasibility Report for Electroplating Zirconium onto Uranium Foil - Year 2

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

Coffey, Greg W.; Meinhardt, Kerry D.; Joshi, Vineet V.

2015-03-01

The Fuel Fabrication Capability within the U.S. High Performance Research Reactor Conversion Program is funded through the National Nuclear Security Administration (NNSA) NA-26 (Office of Material Management and Minimization). An investigation was commissioned to determine the feasibility of using electroplating techniques to apply a coating of zirconium onto depleted uranium/molybdenum alloy (U-10Mo). Electroplating would provide an alternative method to the existing process of hot roll-bonding zirconium foil onto the U-10Mo fuel foil during the fabrication of fuel elements for high-performance research reactors. The objective of this research was to develop a reproducible and scalable plating process that will produce amore » uniform, 25 μm thick zirconium metal coating on U-10Mo foil. In previous work, Pacific Northwest National Laboratory (PNNL) established a molten salt electroplating apparatus and protocol to plate zirconium metal onto molybdenum foil (Coffey 2015). During this second year of the research, PNNL furthered this work by moving to the U-10Mo alloy system (90 percent uranium:10 percent molybdenum). The original plating apparatus was disassembled and re-assembled in a laboratory capable of handling low-level radioactive materials. Initially, the work followed the previous year’s approach, and the salt bath composition was targeted at the eutectic composition (LiF:NaF:ZrF4 = 26:37:37 mol%). Early results indicated that the formation of uranium fluoride compounds would be problematic. Other salt bath compositions were investigated in order to eliminate the uranium fluoride production (LiF:NaF = 61:39 mol% and LiF:NaF:KF = 46.5:11.5:42 mol% ). Zirconium metal was used as the crucible for the molten salt. Three plating methods were used—isopotential, galvano static, and pulsed plating. The molten salt method for zirconium metal application provided high-quality plating on molybdenum in PNNL’s previous work. A key advantage of this approach is

Hopping conduction in zirconium oxynitrides thin film deposited by reactive magnetron sputtering

NASA Astrophysics Data System (ADS)

Guo, Jie; Zhan, Guanghui; Liu, Jingquan; Yang, Bin; Xu, Bin; Feng, Jie; Chen, Xiang; Yang, Chunsheng

2015-10-01

Zirconium oxynitrides thin film thermometers were demonstrated to be useful temperature sensors. However, the basic conduction mechanism of zirconium oxynitrides films has been a long-standing issue, which hinders the prediction and optimization of their ultimate performance. In this letter, zirconium oxynitrides films were grown on sapphire substrates by magnetron sputtering and their electric transport mechanism has been systemically investigated. It was found that in high temperatures region (>150 K) the electrical conductivity was dominated by thermal activation for all samples. In the low temperatures range, while Mott variable hopping conduction (VRH) was dominated the transport for films with relatively low resistance, a crossover from Mott VRH conduction to Efros-Shklovskii (ES) VRH was observed for films with relatively high resistance. This low temperature crossover from Mott to ES VRH indicates the presence of a Coulomb gap (~7 meV). These results demonstrate the competing and tunable conduction mechanism in zirconium oxynitrides thin films, which would be helpful for optimizing the performance of zirconium oxynitrides thermometer.

Lithium aluminate/zirconium material useful in the production of tritium

DOEpatents

Cawley, W.E.; Trapp, T.J.

A composition is described useful in the production of tritium in a nuclear reactor. Lithium aluminate particles are dispersed in a matrix of zirconium. Tritium produced by the reactor of neutrons with the lithium are absorbed by the zirconium, thereby decreasing gas pressure within capsules carrying the material.

Lithium aluminate/zirconium material useful in the production of tritium

DOEpatents

Cawley, W.E.; Trapp, T.J.

1984-10-09

A composition is described useful in the production of tritium in a nuclear reactor. Lithium aluminate particles are dispersed in a matrix of zirconium. Tritium produced by the reactor of neutrons with the lithium are absorbed by the zirconium, thereby decreasing gas pressure within capsules carrying the material.

Lithium aluminate/zirconium material useful in the production of tritium

DOEpatents

Cawley, William E.; Trapp, Turner J.

1984-10-09

A composition is described useful in the production of tritium in a nuclear eactor. Lithium aluminate particles are dispersed in a matrix of zirconium. Tritium produced by the reactor of neutrons with the lithium are absorbed by the zirconium, thereby decreasing gas pressure within capsules carrying the material.

Sensing of NO2 with Zirconium Hydroxide via Electrical Impedance Spectroscopy

NASA Astrophysics Data System (ADS)

Harris, Coleman; Soliz, Jennifer; Klevitch, Andrew; Rossin, Joseph; Fountain, Augustus, III; Peterson, Gregory; Hauser, Adam

Nitrogen Dioxide (NO2) is a brown gas mainly produced as a byproduct of burning fossil fuels, such as automobiles and power plants. Nitrogen oxides can form acid rain and smog by reacting with air, can form toxic organic nitrates by reacting with soil, and can react with oxygen in water, destroying marine life due to a lack of breathable oxygen. Any concentration beyond 53 ppb (air quality standard) can cause irritation to the lungs and respiratory infections, and higher dosages can be fatal. As such, research in NO2 detection is incredibly important to human welfare. Zirconium hydroxide (Zr(OH)4) has been investigated as a candidate NO2 dielectric sensor using impedance spectroscopy analysis. Impedance changes of several orders of magnitude are seen down to our dosage minimum of 50 ppmhr. Changes in impedance correlate with nitrogen and oxygen atomic ratio increases observed via X-ray photoelectron spectroscopy (XPS). The results indicate that Zr(OH)4 may be a strong candidate for use in impedance-based NO2 detection devices. A.J.H., J.R.S., A.W.F. and G.W. P. acknowledge funding under Army Research Office STIR Award #W911F-15-1-0104. J.R.S. acknowledges funding under a NRC fellowship and is advised by Dr. Christopher Karwacki, ECBC.

Anticorrosive Behavior and Porosity of Tricationic Phosphate and Zirconium Conversion Coating on Galvanized Steel

NASA Astrophysics Data System (ADS)

Velasquez, Camilo S.; Pimenta, Egnalda P. S.; Lins, Vanessa F. C.

2018-05-01

This work evaluates the corrosion resistance of galvanized steel treated with tricationic phosphate and zirconium conversion coating after painting, by using electrochemical techniques, accelerated and field corrosion tests. A non-uniform and heterogeneous distribution of zirconium on the steel surface was observed due to preferential nucleation of the zirconium on the aluminum-rich sites on the surface of galvanized steel. The long-term anti-corrosion performance in a saline solution was better for the phosphate coating up to 120 days. The coating capacitance registered a higher increase for the zirconium coatings than the phosphate coatings up to 120 days of immersion. This result agrees with the higher porosity of zirconium coating in relation to the phosphate coating. After 3840 h of accelerated corrosion test, and after 1 year of accelerated field test, zirconium-treated samples showed an average scribe delamination length higher than the phosphate-treated samples.

Anticorrosive Behavior and Porosity of Tricationic Phosphate and Zirconium Conversion Coating on Galvanized Steel

NASA Astrophysics Data System (ADS)

Velasquez, Camilo S.; Pimenta, Egnalda P. S.; Lins, Vanessa F. C.

2018-04-01

This work evaluates the corrosion resistance of galvanized steel treated with tricationic phosphate and zirconium conversion coating after painting, by using electrochemical techniques, accelerated and field corrosion tests. A non-uniform and heterogeneous distribution of zirconium on the steel surface was observed due to preferential nucleation of the zirconium on the aluminum-rich sites on the surface of galvanized steel. The long-term anti-corrosion performance in a saline solution was better for the phosphate coating up to 120 days. The coating capacitance registered a higher increase for the zirconium coatings than the phosphate coatings up to 120 days of immersion. This result agrees with the higher porosity of zirconium coating in relation to the phosphate coating. After 3840 h of accelerated corrosion test, and after 1 year of accelerated field test, zirconium-treated samples showed an average scribe delamination length higher than the phosphate-treated samples.

Photocatalytic activity against azo dye and cytotoxicity on MCF-7 cell lines of zirconium oxide nanoparticle mediated using leaves of Lagerstroemia speciosa.

PubMed

Sai Saraswathi, V; Santhakumar, K

2017-04-01

Metal oxide nanoparticles are gaining interest in recent years. The present paper explains about the green synthesis of zirconium oxide nanoparticles (ZrO NPs) mediated from the leaves of Lagerstroemia speciosa. The prepared ZrO NPs were characterized by UV-vis spectroscopy, FT-IR, X-ray diffraction analysis (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX) and Thermogravimetric Analysis (TGA). The photocatalytic activity of ZrO NPs was studied for azo dye by exposing to sunlight. The azo dye was degraded up to 94.58%. Also the ZrO NPs were studied for in vitro cytotoxicity activity against breast cancer cell lines-MCF-7 and evaluated by MTT assay. The cell morphological changes were recorded by light microscope. The cells viability was seen at 500μg/mL when compared against control. Hence the research highlights, that the method was simple, eco-friendly towards environment by phytoremediation activity of the azo dye and cytotoxicity activity against MCF-7 cell lines. Hence the present paper may help to further explore the metal nanoparticle for its potential applications. Copyright © 2017 Elsevier B.V. All rights reserved.

A Highly Active Low Voltage Redox Mediator for Enhanced Rechargeability of Lithium-Oxygen Batteries.

PubMed

Kundu, Dipan; Black, Robert; Adams, Brian; Nazar, Linda F

2015-12-23

Owing to its high theoretical specific energy, the Li-oxygen battery is one of the fundamentally most promising energy storage systems, but also one of the most challenging. Poor rechargeability, involving the oxidation of insoluble and insulating lithium peroxide (Li2O2), has remained the "Achilles' heel" of this electrochemical energy storage system. We report here on a new redox mediator tris[4-(diethylamino)phenyl]amine (TDPA), that-at 3.1 V-exhibits the lowest and closest potential redox couple compared to the equilibrium voltage of the Li-oxygen cell of those reported to date, with a second couple also at a low potential of 3.5 V. We show it is a soluble "catalyst" capable of lowering the Li2O2 charging potential by >0.8 V without requiring direct electrical contact of the peroxide and that it also facilitates high discharge capacities. Its chemical and electrochemical stability, fast diffusion kinetics, and two dynamic redox potentials represent a significant advance in oxygen-evolution catalysis. It enables Li-O2 cells that can be recharged more than 100 cycles with average round-trip efficiencies >80%, opening a new avenue for practical Li-oxygen batteries.

Protein lysine-Nζ alkylation and O-phosphorylation mediated by DTT-generated reactive oxygen species

PubMed Central

Kumar, Nigam; Ippel, Hans; Weber, Christian; Hackeng, Tilman; Mayo, Kevin H

2013-01-01

Reactive oxygen species (ROS) play crucial roles in physiology and pathology. In this report, we use NMR spectroscopy and mass spectrometry (MS) to demonstrate that proteins (galectin-1, ubiquitin, RNase, cytochrome c, myoglobin, and lysozyme) under reducing conditions with dithiothreitol (DTT) become alkylated at lysine-Nζ groups and O-phosphorylated at serine and threonine residues. These adduction reactions only occur in the presence of monophosphate, potassium, trace metals Fe/Cu, and oxygen, and are promoted by reactive oxygen species (ROS) generated via DTT oxidation. Superoxide mediates the chemistry, because superoxide dismutase inhibits the reaction, and hydroxyl and phosphoryl radicals are also likely involved. While lysine alkylation accounts for most of the adduction, low levels of phosphorylation are also observed at some serine and threonine residues, as determined by western blotting and MS fingerprinting. The adducted alkyl group is found to be a fragment of DTT that forms a Schiff base at lysine Nζ groups. Although its exact chemical structure remains unknown, the DTT fragment includes a SH group and a –CHOH–CH2– group. Chemical adduction appears to be promoted in the context of a well-folded protein, because some adducted sites in the proteins studied are considerably more reactive than others and the reaction occurs to a lesser extent with shorter, unfolded peptides and not at all with small organic molecules. A structural signature involving clusters of positively charged and other polar groups appears to facilitate the reaction. Overall, our findings demonstrate a novel reaction for DTT-mediated ROS chemistry with proteins. PMID:23315912

Isomerization of Cyclooctadiene to Cyclooctyne with a Zinc/Zirconium Heterobimetallic Complex.

PubMed

Butler, Michael J; White, Andrew J P; Crimmin, Mark R

2016-06-06

Reaction of a zinc/zirconium heterobimetallic complex with 1,5-cyclooctadiene (1,5-COD) results in slow isomerization to 1,3-cyclooctadiene (1,3-COD), along with the formation of a new complex that includes a cyclooctyne ligand bridging two metal centers. While analogous magnesium/zirconium and aluminum/zirconium heterobimetallic complexes are competent for the catalytic isomerization of 1,5-COD to 1,3-COD, only in the case of the zinc species is the cyclooctyne adduct observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PHYSICAL PROPERTIES OF ZIRCONIUM NITRIDE IN THE HOMOGENEITY REGION (in Ukrainian)

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

Samsonov, G.V.; Verkhoglyadova, T.S.

1962-01-01

The x-ray method was used to determine the homogeneity region of zirconium nitride as 40 to 50 at.% (9.5 to 13.3% by weight) of nitrogen. It is also shown that part of the ionic bond in the zirconium nitride lattice increases with a decrease in the nitrogen content in this region, this increase being higher than in the homogeneity region of titunium nitride due to the smaller degree of unfilling of the electron d-shell of the zirconium atom in comparison with that of the titanium atom. (auth)

In-situ stabilization of radioactive zirconium swarf

DOEpatents

Hess, C.C.

1999-08-31

The method for treating ignitable cutting swarf in accordance with the present invention involves collecting cutting swarf in a casting mold underwater and injecting a binder mixture comprising vinyl ester styrene into the vessel to fill void volume; and form a mixture comprising swarf and vinyl ester styrene; and curing the mixture. The method is especially useful for stabilizing the ignitable characteristics of radioactive zirconium cutting swarf, and can be used to solidify zirconium swarf, or other ignitable finely divided material, underwater. The process could also be performed out of water with other particulate wastes. 6 figs.

Effect of hydrogenation conditions on the microstructure and mechanical properties of zirconium hydride

NASA Astrophysics Data System (ADS)

Muta, Hiroaki; Nishikane, Ryoji; Ando, Yusuke; Matsunaga, Junji; Sakamoto, Kan; Harjo, Stefanus; Kawasaki, Takuro; Ohishi, Yuji; Kurosaki, Ken; Yamanaka, Shinsuke

2018-03-01

Precipitation of brittle zirconium hydrides deteriorate the fracture toughness of the fuel cladding tubes of light water reactor. Although the hydride embrittlement has been studied extensively, little is known about physical properties of the hydride due to the experimental difficulties. In the present study, to elucidate relationship between mechanical properties and microstructure, two δ-phase zirconium hydrides and one ε-phase zirconium hydride were carefully fabricated considering volume changes at the metal-to-hydride transformation. The δ-hydride that was fabricated from α-zirconium exhibits numerous inner cracks due to the large volume change. Analyses of the neutron diffraction pattern and electron backscatter diffraction (EBSD) data show that the sample displays significant stacking faults in the {111} plane and in the pseudo-layered microstructure. On the other hand, the δ-hydride sample fabricated from β-zirconium at a higher temperature displays equiaxed grains and no cracks. The strong crystal orientation dependence of mechanical properties were confirmed by indentation test and EBSD observation. The δ-hydride hydrogenated from α-zirconium displays a lower Young's modulus than that prepared from β-zirconium. The difference is attributed to stacking faults within the {111} plane, for which the Young's modulus exhibits the highest value in the perpendicular direction. The strong influence of the crystal orientation and dislocation density on the mechanical properties should be considered when evaluating hydride precipitates in nuclear fuel cladding.

PROCESS OF PREPARING ZIRCONIUM OXYCHLORIDE

DOEpatents

Wilhelm, H.A.; Andrews, M.L.

1960-06-28

A process is given for preparing zirconyl chloride by mixing solid zirconyl chloride octahydrate and solid zirconium tetrachloride at room temperature whereby both chlorides are converted to zirconyl chloride trinydrate and hydrogen chloride is formed and volatilized by the reaction heat.

Reactive Oxygen Species-Induced TXNIP Drives Fructose-Mediated Hepatic Inflammation and Lipid Accumulation Through NLRP3 Inflammasome Activation

PubMed Central

Zhang, Xian; Zhang, Jian-Hua; Chen, Xu-Yang; Hu, Qing-Hua; Wang, Ming-Xing; Jin, Rui; Zhang, Qing-Yu; Wang, Wei; Wang, Rong; Kang, Lin-Lin; Li, Jin-Sheng; Li, Meng

2015-01-01

Abstract Aims: Increased fructose consumption predisposes the liver to nonalcoholic fatty liver disease (NAFLD), but the mechanisms are elusive. Thioredoxin-interacting protein (TXNIP) links oxidative stress to NOD-like receptor family, pyrin domain containing 3 (NLRP3) inflammasome activation and this signaling axis may be involved in fructose-induced NAFLD. Here, we explore the role of reactive oxygen species (ROS)-induced TXNIP overexpression in fructose-mediated hepatic NLRP3 inflammasome activation, inflammation, and lipid accumulation. Results: Rats were fed a 10% fructose diet for 8 weeks and treated with allopurinol and quercetin during the last 4 weeks. Five millimolars of fructose-exposed hepatocytes (primary rat hepatocytes, rat hepatic parenchymal cells [RHPCs], HLO2, HepG2) were co-incubated with antioxidants or caspase-1 inhibitor or subjected to TXNIP or NLRP3 siRNA interference. Fructose induced NLRP3 inflammasome activation and pro-inflammatory cytokine secretion, janus-activated kinase 2/signal transducers and activators of transcription 3-mediated inflammatory signaling, and expression alteration of lipid metabolism-related genes in cultured hepatocytes and rat livers. NLRP3 silencing and caspase-1 suppression blocked these effects in primary rat hepatocytes and RHPCs, confirming that inflammasome activation alters hepatocyte lipid metabolism. Hepatocellular ROS and TXNIP were increased in animal and cell models. TXNIP silencing blocked NLRP3 inflammasome activation, inflammation, and lipid metabolism perturbations but not ROS induction in fructose-exposed hepatocytes, whereas antioxidants addition abrogated TXNIP induction and diminished the detrimental effects in fructose-exposed hepatocytes and rat livers. Innovation and Conclusions: This study provides a novel mechanism for fructose-induced NAFLD pathogenesis by which the ROS-TXNIP pathway mediates hepatocellular NLRP3 inflammasome activation, inflammation and lipid accumulation. Antioxidant

Intercalation chemistry of zirconium 4-sulfophenylphosphonate

NASA Astrophysics Data System (ADS)

Svoboda, Jan; Zima, Vítězslav; Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava

2013-12-01

Zirconium 4-sulfophenylphosphonate is a layered material which can be employed as a host for the intercalation reactions with basic molecules. A wide range of organic compounds were chosen to represent intercalation ability of zirconium 4-sulfophenylphosphonate. These were a series of alkylamines from methylamine to dodecylamine, 1,4-phenylenediamine, p-toluidine, 1,8-diaminonaphthalene, 1-aminopyrene, imidazole, pyridine, 4,4‧-bipyridine, poly(ethylene imine), and a series of amino acids from glycine to 6-aminocaproic acid. The prepared compounds were characterized by powder X-ray diffraction, thermogravimetry analysis and IR spectroscopy and probable arrangement of the guest molecules in the interlayer space of the host is proposed based on the interlayer distance of the prepared intercalates and amount of the intercalated guest molecules.

Quantum mechanical calculations suggest that lytic polysaccharide monooxygenases use a copper-oxyl, oxygen-rebound mechanism

PubMed Central

Kim, Seonah; Ståhlberg, Jerry; Sandgren, Mats; Paton, Robert S.; Beckham, Gregg T.

2014-01-01

Lytic polysaccharide monooxygenases (LPMOs) exhibit a mononuclear copper-containing active site and use dioxygen and a reducing agent to oxidatively cleave glycosidic linkages in polysaccharides. LPMOs represent a unique paradigm in carbohydrate turnover and exhibit synergy with hydrolytic enzymes in biomass depolymerization. To date, several features of copper binding to LPMOs have been elucidated, but the identity of the reactive oxygen species and the key steps in the oxidative mechanism have not been elucidated. Here, density functional theory calculations are used with an enzyme active site model to identify the reactive oxygen species and compare two hypothesized reaction pathways in LPMOs for hydrogen abstraction and polysaccharide hydroxylation; namely, a mechanism that employs a η1-superoxo intermediate, which abstracts a substrate hydrogen and a hydroperoxo species is responsible for substrate hydroxylation, and a mechanism wherein a copper-oxyl radical abstracts a hydrogen and subsequently hydroxylates the substrate via an oxygen-rebound mechanism. The results predict that oxygen binds end-on (η1) to copper, and that a copper-oxyl–mediated, oxygen-rebound mechanism is energetically preferred. The N-terminal histidine methylation is also examined, which is thought to modify the structure and reactivity of the enzyme. Density functional theory calculations suggest that this posttranslational modification has only a minor effect on the LPMO active site structure or reactivity for the examined steps. Overall, this study suggests the steps in the LPMO mechanism for oxidative cleavage of glycosidic bonds. PMID:24344312

Derivatization of single-walled carbon nanotubes with redox mediator for biocatalytic oxygen electrodes.

PubMed

Sadowska, K; Stolarczyk, K; Biernat, J F; Roberts, K P; Rogalski, J; Bilewicz, R

2010-11-01

Single-walled carbon nanotubes (SWCNTs) were covalently modified with a redox mediator derived from 2,2'-azino-bis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS), and implemented in the construction of electrodes for biocatalytic oxygen reduction. The procedure is based on: covalent bonding of mediator to nanotubes, placing the nanotubes directly on the carbon electrode surface and covering the nanostructured electrode with a Nafion film containing laccase as the biocatalyst. The modified electrode is stable and the problem of mediator (ABTS) leaking from the film is eliminated by binding it covalently to the nanotubes. Three different synthetic approaches were used to obtain ABTS-modified carbon nanotubes. Nanotubes were modified at ends/defect sites or on the nanotube sidewalls and characterized by Raman spectroscopy, TGA and electrochemistry. The accessibility of differently located ABTS units by the laccase active center and mediation of electron transfer were studied by cyclic voltammetry. The surface concentrations of ABTS groups electrically connected with the electrode were compared for each of the electrodes based on the charges of the voltammetric peaks recorded in the deaerated solution. The nanotube modification procedure giving the best parameters of the catalytic process was selected. Copyright © 2010 Elsevier B.V. All rights reserved.

Growth and characterization of zirconium oxynitride films prepared by reactive direct current magnetron sputtering

NASA Astrophysics Data System (ADS)

Venkataraj, S.; Kappertz, O.; Jayavel, R.; Wuttig, M.

2002-09-01

Thin films of zirconium oxynitrides have been deposited onto Si(100) substrates at room temperature by reactive dc magnetron sputtering of a metallic Zr target in an argon-oxygen-nitrogen atmosphere. To prepare oxynitride films the sum of the O2 and N2 flow was kept at 3.5 sccm, while the relative nitrogen content of this mixture was changed stepwise from 0% to 100%. The film structure was determined by x-ray diffraction, while x-ray reflectometry was employed to determine the thickness, density, and surface roughness of the films. The optical properties have been studied by spectroscopic reflectance measurements. X-ray diffraction (XRD) determines that the as-deposited films are crystalline and do not change their monoclinic ZrO2 crystal structure even for nitrogen flows up to 80%. For pure argon-nitrogen sputtering, on the contrary, cubic zirconium nitride (ZrN) has been formed. Nevertheless, even though the crystal structure does not change with increasing nitrogen flow up to 80%, there is clear evidence from nitrogen incorporation from Rutherford backscattering experiments, optical spectroscopy, XRD, and x-ray reflectometry. The latter technique determines that the film density increases from 5.2 to 5.8 g/cm3 with increasing nitrogen flow from 0% to 80%. Simultaneously, the rate of sputtering increases from 0.17 to 0.6 m/s, while the film roughness decreases upon increasing N2 flow. Optical spectroscopy measurements of the film reflectance confirm that fully transparent films can be prepared up to a nitrogen flow of 80%. For these films, the band gap decreases from 4.52 to 3.59 eV with increasing N2 flow, while the refractive index at 650 nm simultaneously increases from 2.11 to 2.26. For 100% N2 flow, i.e., without any oxygen, films with a metallic reflectance are obtained.

Thermodynamic Analysis and Growth of Zirconium Carbide by Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Wei, Sun; Hua, Hao Zheng; Xiang, Xiong

Equilibrium calculations were used to optimize conditions for the chemical vapor deposition of zirconium carbide from zirconium halide + CxHy+H2+Ar system. The results show the CVD-ZrC phase diagram is divided into ZrC+C, ZrC and ZrC+Zr zones by C, Zr generating lines. For the same mole of ZrCl4 reactant, it needs higher concentration of CH4 to generate single ZrC phase than that of C3H6. Using these calculations as a guide, single-phase cubic zirconium carbide coatings were deposited onto graphite substrate.

Evaluation of a Zirconium Recycle Scrubber System

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

Spencer, Barry B.; Bruffey, Stephanie H.

2017-04-01

A hot-cell demonstration of the zirconium recycle process is planned as part of the Materials Recovery and Waste Forms Development (MRWFD) campaign. The process treats Zircaloy® cladding recovered from used nuclear fuel with chlorine gas to recover the zirconium as volatile ZrCl4. This releases radioactive tritium trapped in the alloy, converting it to volatile tritium chloride (TCl). To meet regulatory requirements governing radioactive emissions from nuclear fuel treatment operations, the capture and retention of a portion of this TCl may be required prior to discharge of the off-gas stream to the environment. In addition to demonstrating tritium removal from amore » synthetic zirconium recycle off-gas stream, the recovery and quantification of tritium may refine estimates of the amount of tritium present in the Zircaloy cladding of used nuclear fuel. To support these objectives, a bubbler-type scrubber was fabricated to remove the TCl from the zirconium recycle off-gas stream. The scrubber was fabricated from glass and polymer components that are resistant to chlorine and hydrochloric acid solutions. Because of concerns that the scrubber efficiency is not quantitative, tests were performed using DCl as a stand-in to experimentally measure the scrubbing efficiency of this unit. Scrubbing efficiency was ~108% ± 3% with water as the scrubber solution. Variations were noted when 1 M NaOH scrub solution was used, values ranged from 64% to 130%. The reason for the variations is not known. It is recommended that the equipment be operated with water as the scrubbing solution. Scrubbing efficiency is estimated at 100%.« less

Extractive separation of uranium and zirconium sulfates by amines

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

Schroetterova, D.; Nekovar, P.; Mrnka, M.

1992-04-01

This paper describes an amine extraction process for zirconium and uranium separation. The behaviour of an extraction system containing uranium (VI) sulfate, zirconium (IV) sulfate, 0.2 and 0.5 M sulfuric acid (as the original aqueous phase), tertiary amine tri-n-lauryl- amine or primary amine Primene JMT in benzene (as the original organic phase) is discussed on the basis of equilibrium data. The measured dependences show that the degree of extraction of zirconium at the sulfuric acid concentration of 0.5 M and above is only slightly affected by a presence of uranium in solution. From this surprising behaviour it follows that zirconiummore » may be employed for the displacement of uranium from the organic phase. This effect is more pronounced with the primary amine Primene JMT than with TLA. 29 refs., 4 figs., 1 tab.« less

21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 7 2013-04-01 2013-04-01 false Use of aerosol cosmetic products containing... SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.16 Use of aerosol cosmetic products containing zirconium. (a) Zirconium-containing complexes have been used as an ingredient...

21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 7 2012-04-01 2012-04-01 false Use of aerosol cosmetic products containing... SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.16 Use of aerosol cosmetic products containing zirconium. (a) Zirconium-containing complexes have been used as an ingredient...

21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 7 2014-04-01 2014-04-01 false Use of aerosol cosmetic products containing... SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.16 Use of aerosol cosmetic products containing zirconium. (a) Zirconium-containing complexes have been used as an ingredient...

From Zirconium Nanograins to Zirconia Nanoneedles

PubMed Central

Zalnezhad, E.; Hamouda, A. M. S.; Jaworski, J.; Do Kim, Young

2016-01-01

Combinations of three simple techniques were utilized to gradually form zirconia nanoneedles from zirconium nanograins. First, a physical vapor deposition magnetron sputtering technique was used to deposit pure zirconium nanograins on top of a substrate. Second, an anodic oxidation was applied to fabricate zirconia nanotubular arrays. Finally, heat treatment was used at different annealing temperatures in order to change the structure and morphology from nanotubes to nanowires and subsequently to nanoneedles in the presence of argon gas. The size of the pure zirconium nanograins was estimated to be approximately 200–300 nm. ZrO2 nanotubular arrays with diameters of 70–120 nm were obtained. Both tetragonal and monoclinic ZrO2 were observed after annealing at 450 °C and 650 °C. Only a few tetragonal peaks appeared at 850 °C, while monoclinic ZrO2 was obtained at 900 °C and 950 °C. In assessing the biocompatibility of the ZrO2 surface, the human cell line MDA-MB-231 was found to attach and proliferate well on surfaces annealed at 850 °C and 450 °C; however, the amorphous ZrO2 surface, which was not heat treated, did not permit extensive cell growth, presumably due to remaining fluoride. PMID:27623486

Molecular Controls of the Oxygenation and Redox Reactions of Hemoglobin

PubMed Central

Henkens, Robert; Alayash, Abdu I.; Banerjee, Sambuddha; Crumbliss, Alvin L.

2013-01-01

Abstract Significance: The broad classes of O2-binding proteins known as hemoglobins (Hbs) carry out oxygenation and redox functions that allow organisms with significantly different physiological demands to exist in a wide range of environments. This is aided by allosteric controls that modulate the protein's redox reactions as well as its O2-binding functions. Recent Advances: The controls of Hb's redox reactions can differ appreciably from the molecular controls for Hb oxygenation and come into play in elegant mechanisms for dealing with nitrosative stress, in the malarial resistance conferred by sickle cell Hb, and in the as-yet unsuccessful designs for safe and effective blood substitutes. Critical Issues: An important basic principle in consideration of Hb's redox reactions is the distinction between kinetic and thermodynamic reaction control. Clarification of these modes of control is critical to gaining an increased understanding of Hb-mediated oxidative processes and oxidative toxicity in vivo. Future Directions: This review addresses emerging concepts and some unresolved questions regarding the interplay between the oxygenation and oxidation reactions of structurally diverse Hbs, both within red blood cells and under acellular conditions. Developing methods that control Hb-mediated oxidative toxicity will be critical to the future development of Hb-based blood substitutes. Antioxid. Redox Signal. 18, 2298–2313. PMID:23198874

A simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys

NASA Technical Reports Server (NTRS)

Dupraw, W. A.

1972-01-01

A simple analytical procedure is described for accurately and precisely determining the zirconium or hafnium content of molybdenum-base alloys. The procedure is based on the reaction of the reagent Arsenazo III with zirconium or hafnium in strong hydrochloric acid solution. The colored complexes of zirconium or hafnium are formed in the presence of molybdenum. Titanium or rhenium in the alloy have no adverse effect on the zirconium or hafnium complex at the following levels in the selected aliquot: Mo, 10 mg; Re, 10 mg; Ti, 1 mg. The spectrophotometric measurement of the zirconium or hafnium complex is accomplished without prior separation with a relative standard deviation of 1.3 to 2.7 percent.

Ultrasound-mediated oxygen delivery from chitosan nanobubbles.

PubMed

Cavalli, Roberta; Bisazza, Agnese; Rolfo, Alessandro; Balbis, Sonia; Madonnaripa, Daniele; Caniggia, Isabella; Guiot, Caterina

2009-08-13

Ultrasound (US) energy combined with gas-filled microbubbles has been used for several years in medical imaging. This study investigated the ability of oxygen-loaded chitosan bubbles to exchange oxygen in the presence or in the absence of US. Oxygen delivery is enhanced by sonication and both frequency and time duration of US affected the exchange kinetics.

Determination of fluoride in water - A modified zirconium-alizarin method

USGS Publications Warehouse

Lamar, W.L.

1945-01-01

A convenient, rapid colorimetric procedure using the zirconium-alizarin indicator acidified with sulfuric acid for the determination of fluoride in water is described. Since this acid indicator is stable indefinitely, it is more useful than other zirconium-alizarin reagents previously reported. The use of sulfuric acid alone in acidifying the zirconium-alizarin reagent makes possible the maximum suppression of the interference of sulfate. Control of the pH of the samples eliminates errors due to the alkalinity of the samples. The fluoride content of waters containing less than 500 parts per million of sulfate and less than 1000 p.p.m. of chloride may be determined within a limit of 0.1 p.p.m. when a 100-ml. sample is used.

Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites.

PubMed

Liu, Chao; Hajagos, Tibor Jacob; Chen, Dustin; Chen, Yi; Kishpaugh, David; Pei, Qibing

2016-02-01

Zirconium oxide nanoparticles are promising candidates for optical engineering, photocatalysis, and high-κ dielectrics. However, reported synthetic methods for the colloidal zirconium oxide nanoparticles use unstable alkoxide precursors and have various other drawbacks, limiting their wide application. Here, we report a facile one-pot method for the synthesis of colloidally stable zirconium oxide nanoparticles. Using a simple solution of zirconium trifluoroacetate in oleylamine, highly stable zirconium oxide nanoparticles have been synthesized with high yield, following a proposed amidization-assisted sol-gel mechanism. The nanoparticles can be readily dispersed in nonpolar solvents, forming a long-term stable transparent solution, which can be further used to fabricate high-refractive-index nanocomposites in both monolith and thin-film forms. In addition, the same method has also been extended to the synthesis of titanium oxide nanoparticles, demonstrating its general applicability to all group IVB metal oxide nanoparticles.

Zirconium Phosphate Supported MOF Nanoplatelets.

PubMed

Kan, Yuwei; Clearfield, Abraham

2016-06-06

We report a rare example of the preparation of HKUST-1 metal-organic framework nanoplatelets through a step-by-step seeding procedure. Sodium ion exchanged zirconium phosphate, NaZrP, nanoplatelets were judiciously selected as support for layer-by-layer (LBL) assembly of Cu(II) and benzene-1,3,5-tricarboxylic acid (H3BTC) linkers. The first layer of Cu(II) is attached to the surface of zirconium phosphate through covalent interaction. The successive LBL growth of HKUST-1 film is then realized by soaking the NaZrP nanoplatelets in ethanolic solutions of cupric acetate and H3BTC, respectively. The amount of assembled HKUST-1 can be readily controlled by varying the number of growth cycles, which was characterized by powder X-ray diffraction and gas adsorption analyses. The successful construction of HKUST-1 on NaZrP was also supported by its catalytic performance for the oxidation of cyclohexene.

Zirconium carbide as an electrocatalyst for the chromous-chromic redox couple

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Reid, M. A.; Yang, C. Y. (Inventor)

1981-01-01

Zirconium carbide is used as a catalyst in a REDOX cell for the oxidation of chromous ions to chromic ions and for the reduction of chromic ions to chromous ions. The zirconium carbide is coated on an inert electronically conductive electrode which is present in the anode fluid of the cell.

Determination of the relative resistance to ignition of selected turbopump materials in high-pressure, high-temperature, oxygen environments, volume 1

NASA Technical Reports Server (NTRS)

Stoltzfus, Joel M.; Benz, Frank J.

1986-01-01

Advances in the design of the liquid oxygen, liquid hydrogen engines for the Space Transportation System call for the use of warm, high-pressure oxygen as the driving gas in the liquid oxygen turbopump. The NASA Lewis Research Center requested the NASA White Sands Test Facility (WSTF) to design a test program to determine the relative resistance to ignition of nine selected turbopump materials: Hastelloy X, Inconel 600, Invar 36, Monel K-500, nickel 200, silicon carbide, stainless steel 316, and zirconium copper. The materials were subjected to particle impact and to frictional heating in high-pressure oxygen.

Superconductivity in zirconium-rhodium alloys

NASA Technical Reports Server (NTRS)

Zegler, S. T.

1969-01-01

Metallographic studies and transition temperature measurements were made with isothermally annealed and water-quenched zirconium-rhodium alloys. The results clarify both the solid-state phase relations at the Zr-rich end of the Zr-Rh alloy system and the influence upon the superconducting transition temperature of structure and composition.

Hyaluronic acid-modified zirconium phosphate nanoparticles for potential lung cancer therapy.

PubMed

Li, Ranwei; Liu, Tiecheng; Wang, Ke

2017-02-01

Novel tumor-targeting zirconium phosphate (ZP) nanoparticles modified with hyaluronic acid (HA) were developed (HA-ZP), with the aim of combining the drug-loading property of ZP and the tumor-targeting ability of HA to construct a tumor-targeting paclitaxel (PTX) delivery system for potential lung cancer therapy. The experimental results indicated that PTX loading into the HA-ZP nanoparticles was as high as 20.36%±4.37%, which is favorable for cancer therapy. PTX-loaded HA-ZP nanoparticles increased the accumulation of PTX in A549 lung cancer cells via HA-mediated endocytosis and exhibited superior anticancer activity in vitro. In vivo anticancer efficacy assay revealed that HA-ZP nanoparticles possessed preferable anticancer abilities, which exhibited minimized toxic side effects of PTX and strong tumor-suppression potential in clinical application.

21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 7 2011-04-01 2010-04-01 true Use of aerosol cosmetic products containing zirconium. 700.16 Section 700.16 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN... and other organs of experimental animals. When used in aerosol form, some zirconium will reach the...

Activation of sperm EGFR by light irradiation is mediated by reactive oxygen species.

PubMed

Shahar, Shiran; Hillman, Pnina; Lubart, Rachel; Ickowicz, Debby; Breitbart, Haim

2014-01-01

To acquire fertilization competence, spermatozoa must undergo several biochemical and motility changes in the female reproductive tract, collectively called capacitation. Actin polymerization and the development of hyperactivated motility (HAM) are part of the capacitation process. In a recent study, we showed that irradiation of human sperm with visible light stimulates HAM through a mechanism involving reactive-oxygen-species (ROS), Ca(2+) influx, protein kinases A (PKA), and sarcoma protein kinase (Src). Here, we showed that this effect of light on HAM is mediated by ROS-dependent activation of the epidermal growth factor receptor (EGFR). Interestingly, ROS-mediated HAM even when the EGFR was activated by EGF, the physiological ligand of EGFR. Light irradiation stimulated ROS-dependent actin polymerization, and this effect was abrogated by PBP10, a peptide which activates the actin-severing protein, gelsolin, and causes actin-depolymerization in human sperm. Light-stimulated tyrosine phosphorylation of Src-dependent gelsolin, resulting in enhanced HAM. Thus, light irradiation stimulates HAM through a mechanism involving Src-mediated actin polymerization. Light-stimulated HAM and in vitro-fertilization (IVF) rate in mouse sperm, and these effects were mediated by ROS and EGFR. In conclusion, we show here that irradiation of sperm with visible light, enhances their fertilization capacity via a mechanism requiring ROS, EGFR and HAM. © 2014 The American Society of Photobiology.

Enhanced oxygen storage capacity of cation-ordered cerium-zirconium oxide induced by titanium substitution.

PubMed

Goto, Yoshihiro; Morikawa, Akira; Iwasaki, Masaoki; Miura, Masahide; Tanabe, Toshitaka

2018-04-03

Herein, we report on the synthesis of Ce0.5Zr0.5-xTixO2 oxygen storage materials prepared via a solution combustion method. Ce0.5Zr0.4Ti0.1O2 showed an outstanding oxygen storage capacity (1310 μmol-O per g) at 200 °C compared to conventional κ-Ce2Zr2O8 (650 μmol-O per g) due to its cation ordering and the formation of weakly bound oxygen atoms induced by Ti substitution.

Method for making fine and ultrafine spherical particles of zirconium titanate and other mixed metal oxide systems

DOEpatents

Hu, Michael Z.

2006-05-23

Disclosed is a method for making amorphous spherical particles of zirconium titanate and crystalline spherical particles of zirconium titanate comprising the steps of mixing an aqueous solution of zirconium salt and an aqueous solution of titanium salt into a mixed solution having equal moles of zirconium and titanium and having a total salt concentration in the range from 0.01 M to about 0.5 M. A stearic dispersant and an organic solvent is added to the mixed salt solution, subjecting the zirconium salt and the titanium salt in the mixed solution to a coprecipitation reaction forming a solution containing amorphous spherical particles of zirconium titanate wherein the volume ratio of the organic solvent to aqueous part is in the range from 1 to 5. The solution of amorphous spherical particles is incubated in an oven at a temperature .ltoreq.100.degree. C. for a period of time .ltoreq.24 hours converting the amorphous particles to fine or ultrafine crystalline spherical particles of zirconium titanate.

Oxygen vacancies mediated ferromagnetism in hydrogenated Zn0.9Co0.1O film

NASA Astrophysics Data System (ADS)

Zhang, Huiyun; Wang, Ji; Cao, Yanqiang; Guo, Xinli; Li, Qi; Du, Jun; Xu, Qingyu

2018-05-01

Zn0.9Co0.1O films were prepared by pulsed laser deposition and followed by annealing treatment in hydrogen atmosphere. Both samples show ferromagnetic behavior and saturated ferromagnetic magnetization was significantly increased by five times after the hydrogenation treatment. Co ions in both samples have been confirmed to be bivalent as substituents. Moreover, hydrogenation did not change the ZnO wurtzite structure and no segregation of Co, Co oxides or any other secondary phases were detected. Furthermore, the Co 2p3/2 peaks shift to lower energy level after hydrogenation, excluding the formation of Co-H-Co complexes. The structural characterizations clearly confirmed that the increment of oxygen vacancies was due to the hydrogenation treatment. These results indicate that the oxygen vacancies play a crucial role in mediating the ferromagnetism in Zn0.9Co0.1O film.

METHOD OF FABRICATING A URANIUM-ZIRCONIUM HYDRIDE REACTOR CORE

DOEpatents

Weeks, I.F.; Goeddel, W.V.

1960-03-22

A method is described of evenly dispersing uranlum metal in a zirconium hydride moderator to produce a fuel element for nuclear reactors. According to the invention enriched uranium hydride and zirconium hydride powders of 200 mesh particle size are thoroughly admixed to form a mixture containing 0.1 to 3% by weight of U/sup 235/ hydride. The mixed powders are placed in a die and pressed at 100 tons per square inch at room temperature. The resultant compacts are heated in a vacuum to 300 deg C, whereby the uranium hydride deoomposes into uranium metal and hydrogen gas. The escaping hydrogen gas forms a porous matrix of zirconium hydride, with uramum metal evenly dispersed therethrough. The advantage of the invention is that the porosity and uranium distribution of the final fuel element can be more closely determined and controlled than was possible using prior methods of producing such fuel ele- ments.

Fretting wear behavior of zirconium alloy in B-Li water at 300 °C

NASA Astrophysics Data System (ADS)

Zhang, Lefu; Lai, Ping; Liu, Qingdong; Zeng, Qifeng; Lu, Junqiang; Guo, Xianglong

2018-02-01

The tangential fretting wear of three kinds of zirconium alloys tube mated with 304 stainless steel (SS) plate was investigated. The tests were conducted in an autoclave containing 300 °C pressurized B-Li water for tube-on-plate contact configuration. The worn surfaces were examined with scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and 3D microscopy. The cross-section of wear scar was examined with transmission electron microscope (TEM). The results indicated that the dominant wear mechanism of zirconium alloys in this test condition was delamination and oxidation. The oxide layer on the fretted area consists of outer oxide layer composed of iron oxide and zirconium oxide and inner oxide layer composed of zirconium oxide.

40 CFR 721.10152 - Oxirane, substituted silylmethyl-, hydrolysis products with alkanol zirconium(4+) salt and silica...

Code of Federal Regulations, 2010 CFR

2010-07-01

...-, hydrolysis products with alkanol zirconium(4+) salt and silica, acetates (generic). 721.10152 Section 721... Oxirane, substituted silylmethyl-, hydrolysis products with alkanol zirconium(4+) salt and silica... zirconium(4+) salt and silica, acetates (PMN P-07-674) is subject to reporting under this section for the...

Aqueous sodium borohydride induced thermally stable porous zirconium oxide for quick removal of lead ions

PubMed Central

Nayak, Nadiya B.; Nayak, Bibhuti B.

2016-01-01

Aqueous sodium borohydride (NaBH4) is well known for its reducing property and well-established for the development of metal nanoparticles through reduction method. In contrary, this research paper discloses the importance of aqueous NaBH4 as a precipitating agent towards development of porous zirconium oxide. The boron species present in aqueous NaBH4 play an active role during gelation as well as phase separated out in the form of boron complex during precipitation, which helps to form boron free zirconium hydroxide [Zr(OH)4] in the as-synthesized condition. Evolved in-situ hydrogen (H2) gas-bubbles also play an important role to develop as-synthesized loose zirconium hydroxide and the presence of intra-particle voids in the loose zirconium hydroxide help to develop porous zirconium oxide during calcination process. Without any surface modification, this porous zirconium oxide quickly adsorbs almost hundred percentages of toxic lead ions from water solution within 15 minutes at normal pH condition. Adsorption kinetic models suggest that the adsorption process was surface reaction controlled chemisorption. Quick adsorption was governed by surface diffusion process and the adsorption kinetic was limited by pore diffusion. Five cycles of adsorption-desorption result suggests that the porous zirconium oxide can be reused efficiently for removal of Pb (II) ions from aqueous solution. PMID:26980545

Reactive Oxygen Species-Mediated Loss of Synaptic Akt1 Signaling Leads to Deficient Activity-Dependent Protein Translation Early in Alzheimer's Disease

PubMed Central

Ahmad, Faraz; Singh, Kunal; Das, Debajyoti; Gowaikar, Ruturaj; Shaw, Eisha; Ramachandran, Arathy; Rupanagudi, Khader Valli; Kommaddi, Reddy Peera; Bennett, David A.

2017-01-01

Abstract Aims: Synaptic deficits are known to underlie the cognitive dysfunction seen in Alzheimer's disease (AD). Generation of reactive oxygen species (ROS) by β-amyloid has also been implicated in AD pathogenesis. However, it is unclear whether ROS contributes to synaptic dysfunction seen in AD pathogenesis and, therefore, we examined whether altered redox signaling could contribute to synaptic deficits in AD. Results: Activity dependent but not basal translation was impaired in synaptoneurosomes from 1-month old presymptomatic APPSwe/PS1ΔE9 (APP/PS1) mice, and this deficit was sustained till middle age (MA, 9–10 months). ROS generation leads to oxidative modification of Akt1 in the synapse and consequent reduction in Akt1-mechanistic target of rapamycin (mTOR) signaling, leading to deficiency in activity-dependent protein translation. Moreover, we found a similar loss of activity-dependent protein translation in synaptoneurosomes from postmortem AD brains. Innovation: Loss of activity-dependent protein translation occurs presymptomatically early in the pathogenesis of AD. This is caused by ROS-mediated loss of pAkt1, leading to reduced synaptic Akt1-mTOR signaling and is rescued by overexpression of Akt1. ROS-mediated damage is restricted to the synaptosomes, indicating selectivity. Conclusions: We demonstrate that ROS-mediated oxidative modification of Akt1 contributes to synaptic dysfunction in AD, seen as loss of activity-dependent protein translation that is essential for synaptic plasticity and maintenance. Therapeutic strategies promoting Akt1-mTOR signaling at synapses may provide novel target(s) for disease-modifying therapy in AD. Antioxid. Redox Signal. 27, 1269–1280. PMID:28264587

Bayesian model selection validates a biokinetic model for zirconium processing in humans

PubMed Central

2012-01-01

Background In radiation protection, biokinetic models for zirconium processing are of crucial importance in dose estimation and further risk analysis for humans exposed to this radioactive substance. They provide limiting values of detrimental effects and build the basis for applications in internal dosimetry, the prediction for radioactive zirconium retention in various organs as well as retrospective dosimetry. Multi-compartmental models are the tool of choice for simulating the processing of zirconium. Although easily interpretable, determining the exact compartment structure and interaction mechanisms is generally daunting. In the context of observing the dynamics of multiple compartments, Bayesian methods provide efficient tools for model inference and selection. Results We are the first to apply a Markov chain Monte Carlo approach to compute Bayes factors for the evaluation of two competing models for zirconium processing in the human body after ingestion. Based on in vivo measurements of human plasma and urine levels we were able to show that a recently published model is superior to the standard model of the International Commission on Radiological Protection. The Bayes factors were estimated by means of the numerically stable thermodynamic integration in combination with a recently developed copula-based Metropolis-Hastings sampler. Conclusions In contrast to the standard model the novel model predicts lower accretion of zirconium in bones. This results in lower levels of noxious doses for exposed individuals. Moreover, the Bayesian approach allows for retrospective dose assessment, including credible intervals for the initially ingested zirconium, in a significantly more reliable fashion than previously possible. All methods presented here are readily applicable to many modeling tasks in systems biology. PMID:22863152

Integral neutron kerma coefficient ratios for silicon, iron, and oxygen to carbon on the energy range from 15 to 30 MeV

NASA Astrophysics Data System (ADS)

Miranda, Juan Gustavo

2001-07-01

Kerma coefficient ratios are reported for carbon to oxygen, silicon, and iron in the energy range of 15 to 30 MeV. The determination was done by measuring dose to the gas of proportional counters exposed to a well characterized neutron field. The measured dose in the proportional counter gas was then converted to dose in the proportional counter wall material applying Bragg-Gray theory. The proportional counters were made of the material of interest. The oxygen measurement was done by irradiating simultaneously zirconium and zirconium oxide proportional counters and substracting the dose to the zirconium from the zirconium oxide. Neutrons were generated with the UW Tandem Accelerator. The reaction 3H(d, n)4 He provided our neutron source which consisted of monoenergetic neutrons. Neutron spectra measurements were carried out for the 27.3 MeV neutron energy. This was necessary because of the presence of contaminating breakup neutrons at this energy. The spectra were measured with a pulse beam time-of-flight spectrometer and a NE-213 liquid scintillator. The dose conversion factor r is reported for carbon, oxygen, silicon, iron, zirconium, and zirconium oxide relative to TE-propane gas at neutron energies of 20, 23 and 27 MeV. The factor r, which relates the dose to the gas to that of the proportional counter through the Bragg-Gray theory, was calculated from angle integrated differential cross sections. This required a calculation of the initial energy spectra as well as the differential secondary charged particle energy spectra and for the first time a complete treatment of all heavy ions is considered. Furthermore, as the conditions required to apply the Bragg-Gray theory are difficult to satisfy (infinitesimal cavity), we report the calculation of the dose conversion factor r for the finite cavity case for carbon/TE-gas in order to test the validity of the application of the theory to this type of applications. We found that the two conditions of the Bragg

Oxygen mobility in CeO{sub 2} and Ce{sub x}Zr({sub 1-x})O{sub 2} compounds: Study by CO transient oxidation and {sup 18}O/{sup 16}O isotopic exchange

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

Madier, Y.; Descorme, C.; Govic, A.M. Le

Cerium-zirconium mixed oxides (Ce{sub x}Zr{sub 1{minus}x}O{sub 2}), precalcined at 900 C in dry air, were supplied by Rhodia Terres Rares as monophasic solid solutions. Introduction of some zirconium atoms in the ceria lattice by isomorphous substitution clearly influences the final properties of these materials as long as the cubic structure of ceria is maintained. Modifications in oxygen storage capacity (OSC measurements), redox properties (CO TPR), and oxygen exchange processes (TPIE) were studied. Ce{sub 0.63}Zr{sub 0.37}O{sub 2} was shown to have the most promising properties with the largest OSC at 400 C and the highest reactivity in O{sub 2} exchange. Allmore » mixed oxides are able to exchange very large amounts of oxygen compared to ceria, implying the participation of bulk oxygen. Furthermore, on Ce{sub x}Zr{sub (1{minus}x)}O{sub 2} samples, oxygen is predominantly exchanged via a multiple heteroexchange mechanism involving surface dioxygen species as superoxides or peroxides.« less

Drug oxygenation activities mediated by liver microsomal flavin-containing monooxygenases 1 and 3 in humans, monkeys, rats, and minipigs.

PubMed

Yamazaki, Miho; Shimizu, Makiko; Uno, Yasuhiro; Yamazaki, Hiroshi

2014-07-15

Liver microsomal flavin-containing monooxygenases (FMO, EC 1.14.13.8) 1 and 3 were functionally characterized in terms of expression levels and molecular catalytic capacities in human, cynomolgus monkey, rat, and minipig livers. Liver microsomal FMO3 in humans and monkeys and FMO1 and FMO3 in rats and minipigs could be determined immunochemically with commercially available anti-human FMO3 peptide antibodies or rat FMO1 peptide antibodies. With respect to FMO-dependent N-oxygenation of benzydamine and tozasertib and S-oxygenation of methimazole and sulindac sulfide activities, rat and minipig liver microsomes had high maximum velocity values (Vmax) and high catalytic efficiency (Vmax/Km, Michaelis constant) compared with those for human or monkey liver microsomes. Apparent Km values for recombinantly expressed rat FMO3-mediated N- and S-oxygenations were approximately 10-100-fold those of rat FMO1, although these enzymes had similar Vmax values. The mean catalytic efficiencies (Vmax/Km, 1.4 and 0.4 min(-1)μM(-1), respectively) of recombinant human and monkey FMO3 were higher than those of FMO1, whereas Vmax/Km values for rat and minipig FMO3 were low compared with those of FMO1. Minipig liver microsomal FMO1 efficiently catalyzed N- and S-oxygenation reactions; in addition, the minipig liver microsomal FMO1 concentration was higher than the levels in rats, humans, and monkeys. These results suggest that liver microsomal FMO1 could contribute to the relatively high FMO-mediated drug N- and S-oxygenation activities in rat and minipig liver microsomes and that lower expression of FMO1 in human and monkey livers could be a determinant factor for species differences in liver drug N- and S-oxygenation activities between experimental animals and humans. Copyright © 2014 Elsevier Inc. All rights reserved.

Application of laser-induced breakdown spectroscopy to zirconium in aqueous solution

NASA Astrophysics Data System (ADS)

Ruas, Alexandre; Matsumoto, Ayumu; Ohba, Hironori; Akaoka, Katsuaki; Wakaida, Ikuo

2017-05-01

In the context of the Fukushima Dai-ichi Nuclear Power Plant (F1-NPP) decommissioning process, laser-induced breakdown spectroscopy (LIBS) has many advantages. The purpose of the present work is to demonstrate the on-line monitoring capability of the LIBS coupled with the ultra-thin liquid jet sampling method. The study focuses on zirconium in aqueous solution, considering that it is a major element in the F1-NPP fuel debris that has been subject to only a few LIBS studies in the past. The methodology of data acquisition and processing are described. In particular, two regions of interest with many high intensity zirconium lines have been observed around 350 nm in the case of the ionic lines and 478 nm in the case of atomic lines. The best analytical conditions for zirconium are different depending on the analysis of ionic lines or atomic lines. A low LOD of about 4 mg L- 1 could be obtained, showing that LIBS coupled with the ultra-thin liquid jet sampling technique is a promising alternative for more complex solutions found in the F1-NPP, namely mixtures containing zirconium.

Five year survival analysis of an oxidised zirconium total knee arthroplasty.

PubMed

Holland, Philip; Santini, Alasdair J A; Davidson, John S; Pope, Jill A

2013-12-01

Zirconium total knee arthroplasties theoretically have a low incidence of failure as they are low friction, hard wearing and hypoallergenic. We report the five year survival of 213 Profix zirconium total knee arthroplasties with a conforming all polyethylene tibial component. Data was collected prospectively and multiple strict end points were used. SF12 and WOMAC scores were recorded pre-operatively, at three months, at twelve months, at 3 years and at 5 years. Eight patients died and six were "lost to follow-up". The remaining 199 knees were followed up for five years. The mean WOMAC score improved from 56 to 35 and the mean SF12 physical component score improved from 28 to 34. The five year survival for failure due to implant related reasons was 99.5% (95% CI 97.4-100). This was due to one tibial component becoming loose aseptically in year zero. Our results demonstrate that the Profix zirconium total knee arthroplasty has a low medium term failure rate comparable to the best implants. Further research is needed to establish if the beneficial properties of zirconium improve long term implant survival. Copyright © 2012 Elsevier B.V. All rights reserved.

Shear Bond Strength of Orthodontic Brackets Bonded to Zirconium Crowns

PubMed Central

Mehmeti, Blerim; Azizi, Bleron; Kelmendi, Jeta; Iljazi-Shahiqi, Donika; Alar, Željko

2017-01-01

Background An increasing demand for esthetic restorations has resulted in an increased use of all-ceramic restorations, such as zirconium. However, one of the challenges the orthodontist must be willing to face is how to increase bond strength between the brackets and various ceramic restorations.Bond strength can beaffected bybracket type, by the material that bracketsaremade of, and their base surface design or retention mode. ​ Aim: of this study was to perform a comparative analysis of the shear bond strength (SBS) of metallic and ceramic orthodontic brackets bonded to all-zirconium ceramic surfaces used for prosthetic restorations, and also to evaluate the fracture mode of these two types of orthodontic brackets. Material and methods Twenty samples/semi-crowns of all-zirconium ceramic, on which orthodontic brackets were bonded, 10 metallic and 10 ceramic polycrystalline brackets, were prepared for this research. SBS has been testedby Universal Testing Machine, with a load applied using a knife edged rod moving at a fixed rate of 1 mm/min, until failure occurred. The force required to debond the brackets was recorded in Newton, then SBS was calculated to MPa. In addition, the samples were analyzed using a digital camera magnifier to determine Adhesive Remnant Index (ARI). Statistical data were processed using t-test, and the level of significance was set at α = 0.05. Results Higher shear bond strength values were observed in metallic brackets bonded to zirconium crowns compared tothoseof ceramic brackets, with a significant difference. During the test, two of the ceramic brackets were partially or totally damaged. Conclusion Metallic brackets, compared to ceramic polycrystalline brackets, seemed tocreate stronger adhesion with all-zirconium surfaces due to their better retention mode. Also, ceramic brackets showed higher fragility during debonding. PMID:28827846

Shear Bond Strength of Orthodontic Brackets Bonded to Zirconium Crowns.

PubMed

Mehmeti, Blerim; Azizi, Bleron; Kelmendi, Jeta; Iljazi-Shahiqi, Donika; Alar, Željko; Anić-Milošević, Sandra

2017-06-01

An increasing demand for esthetic restorations has resulted in an increased use of all-ceramic restorations, such as zirconium. However, one of the challenges the orthodontist must be willing to face is how to increase bond strength between the brackets and various ceramic restorations.Bond strength can beaffected bybracket type, by the material that bracketsaremade of, and their base surface design or retention mode. ​: A im: of this study was to perform a comparative analysis of the shear bond strength (SBS) of metallic and ceramic orthodontic brackets bonded to all-zirconium ceramic surfaces used for prosthetic restorations, and also to evaluate the fracture mode of these two types of orthodontic brackets. Twenty samples/semi-crowns of all-zirconium ceramic, on which orthodontic brackets were bonded, 10 metallic and 10 ceramic polycrystalline brackets, were prepared for this research. SBS has been testedby Universal Testing Machine, with a load applied using a knife edged rod moving at a fixed rate of 1 mm/min, until failure occurred. The force required to debond the brackets was recorded in Newton, then SBS was calculated to MPa. In addition, the samples were analyzed using a digital camera magnifier to determine Adhesive Remnant Index (ARI). Statistical data were processed using t-test, and the level of significance was set at α = 0.05. Higher shear bond strength values were observed in metallic brackets bonded to zirconium crowns compared tothoseof ceramic brackets, with a significant difference. During the test, two of the ceramic brackets were partially or totally damaged. Metallic brackets, compared to ceramic polycrystalline brackets, seemed tocreate stronger adhesion with all-zirconium surfaces due to their better retention mode. Also, ceramic brackets showed higher fragility during debonding.

Mechanical properties of zirconium alloys and zirconium hydrides predicted from density functional perturbation theory

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Tikare, Veena; ...

2015-10-13

Here, the elastic properties and mechanical stability of zirconium alloys and zirconium hydrides have been investigated within the framework of density functional perturbation theory. Results show that the lowest-energy cubic Pn-3m with combining macron]m polymorph of δ-ZrH 1.5 does not satisfy all the Born requirements for mechanical stability, unlike its nearly degenerate tetragonal P4 2/ mcm polymorph. Elastic moduli predicted with the Voigt–Reuss–Hill approximations suggest that mechanical stability of α-Zr, Zr-alloy and Zr-hydride polycrystalline aggregates is limited by the shear modulus. According to both Pugh's and Poisson's ratios, α-Zr, Zr-alloy and Zr-hydride polycrystalline aggregates can be considered ductile. The Debyemore » temperatures predicted for γ-ZrH, δ-ZrH 1.5 and ε-ZrH 2 are θ D = 299.7, 415.6 and 356.9 K, respectively, while θ D = 273.6, 284.2, 264.1 and 257.1 K for the α-Zr, Zry-4, ZIRLO and M5 matrices, i.e. suggesting that Zry-4 possesses the highest micro-hardness among Zr matrices.« less

Role of reactive oxygen species in contraction-mediated glucose transport in mouse skeletal muscle

PubMed Central

Sandström, Marie E; Zhang, Shi-Jin; Bruton, Joseph; Silva, José P; Reid, Michael B; Westerblad, Håkan; Katz, Abram

2006-01-01

Exercise increases glucose transport into skeletal muscle via a pathway that is poorly understood. We investigated the role of endogenously produced reactive oxygen species (ROS) in contraction-mediated glucose transport. Repeated contractions increased 2-deoxyglucose (2-DG) uptake roughly threefold in isolated, mouse extensor digitorum longus (fast-twitch) muscle. N-Acetylcysteine (NAC), a non-specific antioxidant, inhibited contraction-mediated 2-DG uptake by ∼50% (P < 0.05 versus control values), but did not significantly affect basal 2-DG uptake or the uptake induced by insulin, hypoxia or 5-aminoimidazole-4-carboxamide-1-β-d-ribofuranoside (AICAR, which mimics AMP-mediated activation of AMP-activated protein kinase, AMPK). Ebselen, a glutathione peroxidase mimetic, also inhibited contraction-mediated 2-DG uptake (by almost 60%, P < 0.001 versus control values). Muscles from mice overexpressing Mn2+-dependent superoxide dismutase, which catalyses H2O2 production from superoxide anions, exhibited a ∼25% higher rate of contraction-mediated 2-DG uptake versus muscles from wild-type control mice (P < 0.05). Exogenous H2O2 induced oxidative stress, as judged by an increase in the [GSSG]/[GSH + GSSG] (reduced glutathione + oxidized glutathione) ratio to 2.5 times control values, and this increase was substantially blocked by NAC. Similarly, NAC significantly attenuated contraction-mediated oxidative stress as judged by measurements of glutathione status and the intracellular ROS level with the fluorescent indicator 5-(and-6)-chloromethyl-2′,7′-dichlorodihydrofluorescein (P < 0.05). Finally, contraction increased AMPK activity and phosphorylation ∼10-fold, and NAC blocked ∼50% of these changes. These data indicate that endogenously produced ROS, possibly H2O2 or its derivatives, play an important role in contraction-mediated activation of glucose transport in fast-twitch muscle. PMID:16777943

Inhibition of Ice Growth and Recrystallization by Zirconium Acetate and Zirconium Acetate Hydroxide

PubMed Central

Mizrahy, Ortal; Bar-Dolev, Maya; Guy, Shlomit; Braslavsky, Ido

2013-01-01

The control over ice crystal growth, melting, and shaping is important in a variety of fields, including cell and food preservation and ice templating for the production of composite materials. Control over ice growth remains a challenge in industry, and the demand for new cryoprotectants is high. Naturally occurring cryoprotectants, such as antifreeze proteins (AFPs), present one solution for modulating ice crystal growth; however, the production of AFPs is expensive and inefficient. These obstacles can be overcome by identifying synthetic substitutes with similar AFP properties. Zirconium acetate (ZRA) was recently found to induce the formation of hexagonal cavities in materials prepared by ice templating. Here, we continue this line of study and examine the effects of ZRA and a related compound, zirconium acetate hydroxide (ZRAH), on ice growth, shaping, and recrystallization. We found that the growth rate of ice crystals was significantly reduced in the presence of ZRA and ZRAH, and that solutions containing these compounds display a small degree of thermal hysteresis, depending on the solution pH. The compounds were found to inhibit recrystallization in a manner similar to that observed in the presence of AFPs. The favorable properties of ZRA and ZRAH suggest tremendous potential utility in industrial applications. PMID:23555701

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility.

PubMed

Li, H F; Zhou, F Y; Li, L; Zheng, Y F

2016-04-19

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co-Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10(-6) cm(3)·g(-1)-1.29 × 10(-6) cm(3)·g(-1) for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti-6Al-4V, ~3.5 × 10(-6) cm(3)·g(-1), CP Ti and Ti-6Al-7Nb, ~3.0 × 10(-6) cm(3)·g(-1)), and one-sixth that of Co-Cr alloys (Co-Cr-Mo, ~7.7 × 10(-6) cm(3)·g(-1)). Among the Zr-Ru alloy series, Zr-1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr-Ru alloy system as therapeutic devices under MRI diagnostics environments.

Bioactivity and biocompatibility of hydroxyapatite-based bioceramic coatings on zirconium by plasma electrolytic oxidation.

PubMed

Aktuğ, Salim Levent; Durdu, Salih; Yalçın, Emine; Çavuşoğlu, Kültigin; Usta, Metin

2017-02-01

In the present work, hydroxyapatite (HAP)-based plasma electrolytic oxide (PEO) coatings were produced on zirconium at different current densities in a solution containing calcium acetate and β-calcium glycerophosphate by a single step. The phase structure, surface morphology, functional groups, thickness and roughness of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), eddy current method and surface profilometer, respectively. The phases of cubic-zirconia, calcium zirconate and HAP were detected by XRD. The amount of HAP and calcium zirconate increased with increasing current density. The surface of the coatings was very porous and rough. Moreover, bioactivity and biocompatibility of the coatings were analyzed in vitro immersion simulated body fluid (SBF) and MTT (3-(4,5-dimethyl thiazol-2yl)-2,5-diphenyl tetrazolium bromide) assay, hemolysis assay and bacterial formation. The apatite-forming ability of the coatings was evaluated after immersion in SBF up to 28days. After immersion, the bioactivity of HAP-based coatings on zirconium was greater than the ones of uncoated zirconium and zirconium oxide-based surface. The bioactivity of PEO surface on zirconium was significantly improved under SBF conditions. The bacterial adhesion of the coatings decreased with increasing current density. The bacterial adhesion of the coating produced at 0.370A/cm 2 was minimum compared to uncoated zirconium coated at 0.260 and 0.292A/cm 2 . The hemocompatibility of HAP-based surfaces was improved by PEO. The cell attachment and proliferation of the PEO coatings were better than the one of uncoated zirconium according to MTT assay results. Copyright © 2016 Elsevier B.V. All rights reserved.

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

PubMed Central

Li, H.F.; Zhou, F.Y.; Li, L.; Zheng, Y.F.

2016-01-01

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10−6 cm3·g−1–1.29 × 10−6 cm3·g−1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10−6 cm3·g−1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10−6 cm3·g−1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10−6 cm3·g−1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

Ferrier rearrangement promoted by an electrochemically generated zirconium catalyst.

PubMed

Stevanović, Dragana; Pejović, Anka; Damljanović, Ivan; Minić, Aleksandra; Bogdanović, Goran A; Vukićević, Mirjana; Radulović, Niko S; Vukićević, Rastko D

2015-04-30

In situ generated zirconium catalyst from a sacrificial zirconium anode was successfully applied to promote Ferrier rearrangement of 3,4,5-tri-O-acetyl-D-glucal and 6-deoxy-3,4-di-O-acetyl-L-glucal (3,4-di-O-acetyl-L-rhamnal) in the presence of three thiols and eleven thiophenols as nucleophiles. A simple constant current electrolysis (20 mA, 0.4 F mol(-1)) of an acetonitrile solution of lithium perchlorate (0.1 M) containing the corresponding glycal and S-nucleophiles, using a zirconium anode and a platinum cathode resulted in the successful synthesis of the corresponding 2,3-unsaturated peracetylated thioglycosides (with an average anomer ratio α/β=4.129 in the case of peracetylated D-glucal and 8.740 in the case of L-rhamnal). The same procedure proved to be appropriate in synthesizing dihydropyran derivatives ('C-glycosides') using allyltrimethylsilane as the nucleophile (only 'α-anomers' were obtained). All new compounds were fully characterized by spectral data, whereas single-crystal X-ray analysis was performed for two thioglycosides. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solid-phase zirconium and fluoride species in alkaline zircaloy cladding waste at Hanford.

PubMed

Reynolds, Jacob G; Huber, Heinz J; Cooke, Gary A; Pestovich, John A

2014-08-15

The United States Department of Energy Hanford Site, near Richland, Washington, USA, processed plutonium between 1944 and 1987. Fifty-six million gallons of waste of various origins remain, including waste from removing zircaloy fuel cladding using the so-called Zirflex process. The speciation of zirconium and fluoride in this waste is important because of the corrosivity and reactivity of fluoride as well as the (potentially) high density of Zr-phases. This study evaluates the solid-phase speciation of zirconium and fluoride using X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). Two waste samples were analyzed: one waste sample that is relatively pure zirconium cladding waste from tank 241-AW-105 and another that is a blend of zirconium cladding wastes and other high-level wastes from tank 241-C-104. Villiaumite (NaF) was found to be the dominant fluoride species in the cladding waste and natrophosphate (Na7F[PO4]2 · 19H2O) was the dominant species in the blended waste. Most zirconium was present as a sub-micron amorphous Na-Zr-O phase in the cladding waste and a Na-Al-Zr-O phase in the blended waste. Some zirconium was present in both tanks as either rounded or elongated crystalline needles of Na-bearing ZrO2 that are up to 200 μm in length. These results provide waste process planners the speciation data needed to develop disposal processes for this waste. Copyright © 2014 Elsevier B.V. All rights reserved.

Zirconium-based alloys, nuclear fuel rods and nuclear reactors including such alloys, and related methods

DOEpatents

Mariani, Robert Dominick

2014-09-09

Zirconium-based metal alloy compositions comprise zirconium, a first additive in which the permeability of hydrogen decreases with increasing temperatures at least over a temperature range extending from 350.degree. C. to 750.degree. C., and a second additive having a solubility in zirconium over the temperature range extending from 350.degree. C. to 750.degree. C. At least one of a solubility of the first additive in the second additive over the temperature range extending from 350.degree. C. to 750.degree. C. and a solubility of the second additive in the first additive over the temperature range extending from 350.degree. C. to 750.degree. C. is higher than the solubility of the second additive in zirconium over the temperature range extending from 350.degree. C. to 750.degree. C. Nuclear fuel rods include a cladding material comprising such metal alloy compositions, and nuclear reactors include such fuel rods. Methods are used to fabricate such zirconium-based metal alloy compositions.

The 5-year Results of an Oxidized Zirconium Femoral Component for TKA

PubMed Central

Innocenti, Massimo; Carulli, Christian; Matassi, Fabrizio; Villano, Marco

2009-01-01

Osteolysis secondary to polyethylene wear is one of the major factors limiting long-term performance of TKA. Oxidized zirconium is a new material that combines the strength of a metal with the wear properties of a ceramic. It remains unknown whether implants with a zirconium femoral component can be used safely in TKA. To answer that question, we reviewed, at a minimum of 5 years, the clinical outcome and survivorship of a ceramic-surfaced oxidized zirconium femoral component implanted during 98 primary TKAs between April 2001 and December 2003. Survivorship was 98.7% at 7 years postoperatively. No revision was necessary and only one component failed because of aseptic loosening. Mean Knee Society score improved from 36 to 89. No adverse events were observed clinically or radiologically. These results justify pursuing the use of oxidized zirconium as an alternative bearing surface for a femoral component in TKA. Level of Evidence: Level IV, therapeutic study. See Guidelines for Authors for a complete description of levels of evidence. PMID:19798541

Reactive oxygen species mediate pollen tube rupture to release sperm for fertilization in Arabidopsis

NASA Astrophysics Data System (ADS)

Duan, Qiaohong; Kita, Daniel; Johnson, Eric A.; Aggarwal, Mini; Gates, Laura; Wu, Hen-Ming; Cheung, Alice Y.

2014-01-01

In flowering plants, sperm are transported inside pollen tubes to the female gametophyte for fertilization. The female gametophyte induces rupture of the penetrating pollen tube, resulting in sperm release and rendering them available for fertilization. Here we utilize the Arabidopsis FERONIA (FER) receptor kinase mutants, whose female gametophytes fail to induce pollen tube rupture, to decipher the molecular mechanism of this critical male-female interactive step. We show that FER controls the production of high levels of reactive oxygen species at the entrance to the female gametophyte to induce pollen tube rupture and sperm release. Pollen tube growth assays in vitro and in the pistil demonstrate that hydroxyl free radicals are likely the most reactive oxygen molecules, and they induce pollen tube rupture in a Ca2+-dependent process involving Ca2+ channel activation. Our results provide evidence for a RHO GTPase-based signalling mechanism to mediate sperm release for fertilization in plants.

Reactive oxygen species mediate pollen tube rupture to release sperm for fertilization in Arabidopsis.

PubMed

Duan, Qiaohong; Kita, Daniel; Johnson, Eric A; Aggarwal, Mini; Gates, Laura; Wu, Hen-Ming; Cheung, Alice Y

2014-01-01

In flowering plants, sperm are transported inside pollen tubes to the female gametophyte for fertilization. The female gametophyte induces rupture of the penetrating pollen tube, resulting in sperm release and rendering them available for fertilization. Here we utilize the Arabidopsis FERONIA (FER) receptor kinase mutants, whose female gametophytes fail to induce pollen tube rupture, to decipher the molecular mechanism of this critical male-female interactive step. We show that FER controls the production of high levels of reactive oxygen species at the entrance to the female gametophyte to induce pollen tube rupture and sperm release. Pollen tube growth assays in vitro and in the pistil demonstrate that hydroxyl free radicals are likely the most reactive oxygen molecules, and they induce pollen tube rupture in a Ca(2+)-dependent process involving Ca(2+) channel activation. Our results provide evidence for a RHO GTPase-based signalling mechanism to mediate sperm release for fertilization in plants.

Calcification of MC3T3-E1 cells on titanium and zirconium.

PubMed

Umezawa, Takayuki; Chen, Peng; Tsutsumi, Yusuke; Doi, Hisashi; Ashida, Maki; Suzuki, Shoichi; Moriyama, Keiji; Hanawa, Takao

2015-01-01

To confirm similarity of hard tissue compatibility between titanium and zirconium, calcification of MC3T3-E1 cells on titanium and zirconium was evaluated in this study. Mirror-polished titanium (Ti) and zirconium (Zr) disks and zirconium-sputter deposited titanium (Zr/Ti) were employed in this study. The surface of specimens were characterized using scanning electron microscopy and X-ray diffraction. Then, the cellular proliferation, differentiation and calcification of MC3T3-E1 cells on specimens were investigated. The surface of Zr/Ti was much smoother and cleaner than those of Ti and Zr. The proliferation of the cell was the same among three specimens, while the differentiation and calcification on Zr/Ti were faster than those on Ti and Zr. Therefore, Ti and Zr showed the identical hard tissue compatibility according to the evaluation with MC3T3-E1 cells. Sputter deposition may improve cytocompatibility.

Oxygen and Oxygen Toxicity: The Birth of Concepts

PubMed Central

Zhu, Hong; Traore, Kassim; Santo, Arben; Trush, Michael A.; Li, Y. Robert

2018-01-01

Molecular dioxygen (O2) is an essential element of aerobic life, yet incomplete reduction or excitation of O2 during aerobic metabolisms generates diverse oxygen-containing reactive species, commonly known as reactive oxygen species (ROS). On the one hand, ROS pose a serious threat to aerobic organisms via inducing oxidative damage to cellular constituents. On the other hand, these reactive species, when their generation is under homeostatic control, also play important physiological roles (e.g., constituting an important component of immunity and participating in redox signaling). This article defines oxygen and the key facts about oxygen, and discusses the relationship between oxygen and the emergence of early animals on Earth. The article then describes the discovery of oxygen by three historical figures and examines the birth of the concepts of oxygen toxicity and the underlying free radical mechanisms. The article ends with a brief introduction to the emerging field of ROS-mediated redox signaling and physiological responses. PMID:29707642

PROCESS OF RECOVERING ZIRCONIUM VALUES FROM HAFNIUM VALUES BY SOLVENT EXTRACTION WITH AN ALKYL PHOSPHATE

DOEpatents

Peppard, D.F.

1960-02-01

A process of separating hafnium nitrate from zirconium nitrate contained in a nitric acid solution by selectively. extracting the zirconium nitrate with a water-immiscible alkyl phosphate is reported.

Polymer Electrolyte Fuel Cells Employing Heteropolyacids as Redox Mediators for Oxygen Reduction Reactions: Pt-Free Cathode Systems.

PubMed

Matsui, Toshiaki; Morikawa, Eri; Nakada, Shintaro; Okanishi, Takeou; Muroyama, Hiroki; Hirao, Yoshifumi; Takahashi, Tsuyoshi; Eguchi, Koichi

2016-07-20

In this study, the heteropolyacids of H3+xPVxMO12-xO40 (x = 0, 2, and 3) were applied as redox mediators for the oxygen reduction reaction in polymer electrolyte fuel cells, of which the cathode is free from the usage of noble metals such as Pt/C. In this system, the electrochemical reduction of heteropolyacid over the carbon cathode and the subsequent reoxidation of the partially reduced heteropolyacid by exposure to the dissolved oxygen in the regenerator are important processes for continuous power generation. Thus, the redox properties of catholytes containing these heteropolyacids were investigated in detail. The substitution quantity of V in the heteropolyacid affected the onset reduction potential as well as the reduction current density, resulting in a difference in cell performance. The chemical composition of heteropolyacid also had a significant impact on the reoxidation property. Among the three compounds, H6PV3Mo9O40 was the most suitable redox mediator. Furthermore, the pH of the catholyte was found to be the crucial factor in determining the reoxidation rate of partially reduced heteropolyacid as well as cell performance.

About structural phase state of coating based on zirconium oxide formed by microplasma oxidation method

NASA Astrophysics Data System (ADS)

Gubaidulina, Tatiana A.; Sergeev, Viktor P.; Kuzmin, Oleg S.; Fedorischeva, Marina V.; Kalashnikov, Mark P.

2017-12-01

The oxide-ceramic coating based of zirconium oxide is formed by the method of microplasma oxidation. The producing modes of the oxide layers on E110 zirconium alloy are under testing. It was found that using microplasma treatment of E110 zirconium in aluminosilicate electrolyte makes possible the formation of porous oxide-ceramic coatings based on zirconium alloyed by aluminum and niobium. The study is focused on the modes how to form heat-shielding coatings with controlled porosity and minimal amount of microcracks. The structural-phase state of the coating is studied by X-ray diffraction analysis and scanning electron microscopy (SEM). It was found that the ratio of the monoclinic and tetragonal phases changes with the change occurring in the coating formation modes.

Analysis of the influence of the macro- and microstructure of dental zirconium implants on osseointegration: a minipig study.

PubMed

Mueller, Cornelia Katharina; Solcher, Philipp; Peisker, Andrè; Mtsariashvilli, Maia; Schlegel, Karl Andreas; Hildebrand, Gerhard; Rost, Juergen; Liefeith, Klaus; Chen, Jiang; Schultze-Mosgau, Stefan

2013-07-01

It was the aim of this study to analyze the influence of implant design and surface topography on the osseointegration of dental zirconium implants. Six different implant designs were tested in the study. Nine or 10 test implants were inserted in the frontal skull in each of 10 miniature pigs. Biopsies were harvested after 2 and 4 months and subjected to microradiography. No significant differences between titanium and zirconium were found regarding the microradiographically detected bone-implant contact (BIC). Cylindric zirconium implants showed a higher BIC at the 2-month follow-up than conic zirconium implants. Among zirconium implants, those with an intermediate Ra value showed a significantly higher BIC compared with low and high Ra implants 4 months after surgery. Regarding osseointegration, titanium and zirconium showed equal properties. Cylindric implant design and intermediate surface roughness seemed to enhance osseointegration. Copyright © 2013 Elsevier Inc. All rights reserved.

ZIRCONIUM PHOSPHATE ADSORPTION METHOD

DOEpatents

Russell, E.R.; Adamson, A.S.; Schubert, J.; Boyd, G.E.

1958-11-01

A method is presented for separating plutonium values from fission product values in aqueous acidic solution. This is accomplished by flowing the solutlon containing such values through a bed of zirconium orthophosphate. Any fission products adsorbed can subsequently be eluted by washing the column with a solution of 2N HNO/sub 3/ and O.lN H/sub 3/PO/sub 4/. Plutonium values may subsequently be desorbed by contacting the column with a solution of 7N HNO/sub 3/ .

Generation of reactive oxygen species by a novel berberine–bile acid analog mediates apoptosis in hepatocarcinoma SMMC-7721 cells

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

Li, Qingyong, E-mail: li_qingyong@126.com; Zhang, Li; Zu, Yuangang

2013-04-19

Graphical abstract: - Highlights: • Anticancer effects of B4, a novel berberine–bile acid analog, were tested. • B4 inhibited cell proliferation in hepatocellular carcinoma cells. • It also stimulated mitochondrial ROS production and membrane depolarization. • Effects of B4 were inhibited by a non-specific ROS scavenger. • Regulation of ROS generation may be a strategy for treating hepatic carcinoma. - Abstract: 2,3-Methenedioxy-9-O-(3′α,7′α-dihydroxy-5′β-cholan-24′-propy-lester) berberine (B4) is a novel berberine–bile acid analog synthesized in our laboratory. Previously, we showed that B4 exerted greater cytotoxicity than berberine in several human cancer cell lines. Therefore, we further evaluated the mechanism governing its anticancer actionsmore » in hepatocellular carcinoma SMMC-7721 cells. B4 inhibited the proliferation of SMMC-7721 cells, and stimulated reactive oxygen species (ROS) production and mitochondrial membrane depolarization; anti-oxidant capacity was reduced. B4 also induced the release of cytochrome c from the mitochondria to the cytosol and an increase in poly ADP-ribose polymerase (PARP) cleavage products, reflective of caspase-3 activation. Moreover, B4 induced the nuclear translocation of apoptosis-inducing factor (AIF) and a rise in DNA fragmentation. Pretreatment with the anti-oxidant N-acetylcysteine (NAC) inhibited B4-mediated effects, including cytotoxicity, ROS production, mitochondrial membrane depolarization increase in intracellular Ca{sup 2+}, cytochrome c release, PARP cleavage, and AIF translocation. Our data suggest that B4 induces ROS-triggered caspase-dependent and caspase-independent apoptosis pathways in SMMC-7721 cells and that ROS production may be a specific potential strategy for treating hepatic carcinoma.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

PubMed Central

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; Li, Jinyang; Schwab, Mark J.; Brudvig, Gary W.; Taylor, André D.

2016-01-01

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme's oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage. PMID:27759005

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

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

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

DOE PAGES

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; ...

2016-10-19

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

PRECIPITATION OF ZIRCONIUM AND FLUORIDE IONS FROM SOLUTIONS

DOEpatents

Newby, B.J.

1963-06-11

A process is given for removing zirconium and fluorine ions from aqueous solutions also containing uranium(VI). The precipitation is carried out with sodium formate, and the uranium remains in solution. (AEC)

Reactivity of zirconium basic sulfate in the reactions with carbonate, oxalate, and phosphate reagents

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

Nekhamkin, L.G.; Kondrashova, I.A.; Kerina, V.R.

1987-08-20

The reactivity of zirconium basic sulfate is determined by the possibility of replacement of oxo- and hydroxo-ligands and decreases with increasing temperature of its precipitation. The interaction of the less reactive zirconium basic sulfate with carbonate and oxalate reagents occurs at 25/sup 0/C without any change in basicity and that with phosphate reagents occurs with a decrease in it, up to the formation of a monophosphate with basicity about 20%. In the interaction of the more reactive zirconium basic sulfate, obtained without heating, oxo- and hydroxo groups can be entirely replaced by acido-ligands with the formation of unhydrolyzed compounds.

Oceanic Uptake of Oxygen During Deep Convection Events Through Diffusive and Bubble-Mediated Gas Exchange

NASA Astrophysics Data System (ADS)

Sun, Daoxun; Ito, Takamitsu; Bracco, Annalisa

2017-10-01

The concentration of dissolved oxygen (O2) plays fundamental roles in diverse chemical and biological processes throughout the oceans. The balance between the physical supply and the biological consumption controls the O2 level of the interior ocean, and the O2 supply to the deep waters can only occur through deep convection in the polar oceans. We develop a theoretical framework describing the oceanic O2 uptake during open-ocean deep convection events and test it against a suite of numerical sensitivity experiments. Our framework allows for two predictions, confirmed by the numerical simulations. First, both the duration and the intensity of the wintertime cooling contribute to the total O2 uptake for a given buoyancy loss. Stronger cooling leads to deeper convection and the oxygenation can reach down to deeper depths. Longer duration of the cooling period increases the total amount of O2 uptake over the convective season. Second, the bubble-mediated influx of O2 tends to weaken the diffusive influx by shifting the air-sea disequilibrium of O2 toward supersaturation. The degree of compensation between the diffusive and bubble-mediated gas exchange depends on the dimensionless number measuring the relative strength of oceanic vertical mixing and the gas transfer velocity. Strong convective mixing, which may occur under strong cooling, reduces the degree of compensation so that the two components of gas exchange together drive exceptionally strong oceanic O2 uptake.

Preparation of lead-zirconium-titanium film and powder by electrodeposition

DOEpatents

Bhattacharya, Raghu N.; Ginley, David S.

1995-01-01

A process for the preparation of lead-zirconium-titanium (PZT) film and powder compositions. The process comprises the steps of providing an electrodeposition bath, providing soluble salts of lead, zirconium and titanium metals to this bath, electrically energizing the bath to thereby direct ions of each respective metal to a substrate electrode and cause formation of metallic particles as a recoverable film of PZT powder on the electrode, and also recovering the resultant film as a powder. Recovery of the PZT powder can be accomplished by continually energizing the bath to thereby cause powder initially deposited on the substrate-electrode to drop therefrom into the bath from which it is subsequently removed. A second recovery alternative comprises energizing the bath for a period of time sufficient to cause PZT powder deposition on the substrate-electrode only, from which it is subsequently recovered. PZT film and powder so produced can be employed directly in electronic applications, or the film and powder can be subsequently oxidized as by an annealing process to thereby produce lead-zirconium-titanium oxide for use in electronic applications.

METHOD AND ALLOY FOR BONDING TO ZIRCONIUM

DOEpatents

McCuaig, F.D.; Misch, R.D.

1960-04-19

A brazing alloy can be used for bonding zirconium and its alloys to other metals, ceramics, and cermets, and consists of 6 to 9 wt.% Ni, 6 to 9 wn~.% Cr, Mo, or W, 0 to 7.5 wt.% Fe, and the balance Zr.

Characterization of zirconium carbides using electron microscopy, optical anisotropy, Auger depth profiles, X-ray diffraction, and electron density calculated by charge flipping method

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

Chinthaka Silva, G.W., E-mail: chinthaka.silva@gmail.com; Kercher, Andrew A., E-mail: rokparent@comcast.net; Hunn, John D., E-mail: hunnjd@ornl.gov

2012-10-15

Samples with five different zirconium carbide compositions (C/Zr molar ratio=0.84, 0.89, 0.95, 1.05, and 1.17) have been fabricated and studied using a variety of experimental techniques. Each sample was zone refined to ensure that the end product was polycrystalline with a grain size of 10-100 {mu}m. It was found that the lattice parameter was largest for the x=0.89 composition and smallest for the x=1.17 total C/Zr composition, but was not linear; this nonlinearity is possibly explained using electron densities calculated using charge flipping technique. Among the five samples, the unit cell of the ZrC{sub 0.89} sample showed the highest electronmore » density, corresponding to the highest carbon incorporation and the largest lattice parameter. The ZrC{sub 0.84} sample showed the lowest carbon incorporation, resulting in a larger number of carbon vacancies and resultant strain. Samples with larger carbon ratios (x=0.95, 1.05, and 1.17) showed a slight decrease in lattice parameter, due to a decrease in electron density. Optical anisotropy measurements suggest that these three samples contained significant amounts of a graphitic carbon phase, not bonded to the Zr atoms. - Graphical abstract: Characterization of zirconium carbides using electron microscopy, optical anisotropy, Auger depth profiles, X-ray diffraction, and electron density calculated by the charge flipping method. Highlights: Black-Right-Pointing-Pointer The lattice parameter variation: ZrC{sub 0.89}>ZrC{sub 0.84}>ZrC{sub 0.95}>ZrC{sub 1.05}>ZrC{sub 1.17}. Black-Right-Pointing-Pointer Surface oxygen with no correlation to the lattice parameter variation. Black-Right-Pointing-Pointer ZrC{sub 0.89} had highest electron densities correspond to highest carbon incorporation. Black-Right-Pointing-Pointer Second highest lattice parameter in ZrC{sub 0.84} due to strain. Black-Right-Pointing-Pointer Unit cell electron density order: ZrC{sub 0.95}>ZrC{sub 1.05}>ZrC{sub 1.17}.« less

Monochloro non-bridged half-metallocene-type zirconium complexes containing phosphine oxide-(thio)phenolate chelating ligands as efficient ethylene polymerization catalysts.

PubMed

Tang, Xiao-Yan; Wang, Yong-Xia; Liu, San-Rong; Liu, Jing-Yu; Li, Yue-Sheng

2013-01-14

A series of novel monochloro half-zirconocene complexes containing phosphine oxide-(thio)phenolate chelating ligands of the type, ClCp'Zr[X-2-R(1)-4-R(2)-6-(Ph(2)P=O)C(6)H(2)](2) (Cp' = C(5)H(5), 2a: X = O, R(1) = Ph, R(2) = H; 2b: X = O, R(1) = F, R(2) = H; 2c: X = O, R(1) = (t)Bu, R(2) = H; 2d: X = O, R(1) = R(2) = (t)Bu; 2e: X = O, R(1) = SiMe(3), R(2) = H; 2f: X = S, R(1) = SiMe(3), R(2) = H; Cp' = C(5)Me(5), 2g: X = O, R(1) = SiMe(3), R(2) = H), have been synthesized in high yields. These complexes were identified by (1)H {(13)C} NMR and elemental analyses. Structures for 2b, 2c and 2f were further confirmed by X-ray crystallography. Structural characterization of these complexes reveals crowded environments around the zirconium. Complexes 2b and 2c adopt six-coordinate, distorted octahedral geometry around the zirconium center, in which the equatorial positions are occupied by three oxygen atoms of two chelating phosphine oxide-bridged phenolate ligands and a chlorine atom. The cyclopentadienyl ring and one oxygen atom of the ligand are coordinated on the axial position. Complex 2f also folds a six-coordinate, distorted octahedral geometry around the Zr center, consisting of a Cp-Zr-O (in P=O) axis [177.16°] and a distorted plane of two sulfur atoms and one oxygen atom of two chelating phosphine oxide-bridged thiophenolate ligands as well as a chlorine atom. When activated by modified methylaluminoxane (MMAO), all the complexes exhibited high activities towards ethylene polymerization at high temperature (75 °C), giving high molecular weight polymers with unimodal molecular weight distribution. The formation of 14-electron, cationic metal alkyl species might come from the Zr-O (in phenol ring) bond cleavage based on the DFT calculations study.

Heptachlor induced mitochondria-mediated cell death via impairing electron transport chain complex III

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

Hong, Seokheon; Kim, Joo Yeon; Hwang, Joohyun

Highlights: •Heptachlor inhibited mitochondrial electron transport chain complex III activity. •Heptachlor promoted generation of reactive oxygen species. •Heptachlor induced Bax activation. •Heptachlor induced mitochondria-mediated and caspase-dependent apoptosis. -- Abstract: Environmental toxins like pesticides have been implicated in the pathogenesis of Parkinson’s disease (PD). Epidemiological studies suggested that exposures to organochlorine pesticides have an association with an increased PD risk. In the present study, we examined the mechanism of toxicity induced by an organochlorine pesticide heptachlor. In a human dopaminergic neuroblastoma SH-SY5Y cells, heptachlor induced both morphological and functional damages in mitochondria. Interestingly, the compound inhibited mitochondrial electron transport chain complexmore » III activity. Rapid generation of reactive oxygen species and the activation of Bax were then detected. Subsequently, mitochondria-mediated, caspase-dependent apoptosis followed. Our results raise a possibility that an organochlorine pesticide heptachlor can act as a neurotoxicant associated with PD.« less

Zirconium amine tris(phenolate): A more effective initiator for biomedical lactide.

PubMed

Jones, Matthew D; Wu, Xujun; Chaudhuri, Julian; Davidson, Matthew G; Ellis, Marianne J

2017-11-01

Here a zirconium amine tris(phenolate) is used as the initiator for the production of polylactide for biomedical applications, as a replacement for a tin initiator (usually tin octanoate). The ring opening polymerization (ROP) was carried out in the melt at 130°C. The zirconium-catalyzed PLA (PLA-Zr) required 30min, resulting in a polydispersity index (PDI) of 1.17, compared to 1h and PDI=1.77 for tin-catalyzed PLA (PLA-Sn). PLA-Zr and PLA-Sn supported osteosarcoma cell (MG63) culture to the same extent (cell number, morphology, extracellular matrix production and osteogenic function) until day 14 when the PLA-Zr showed increased cell number, overall extracellular matrix production and osteogenic function. To conclude, the reduction in reaction time, controllable microstructure and biologically benign nature of the zirconium amine tris(phenolate) initiator shows that it is a more effective initiator for ROP of polylactide for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Optical fiber-mediated photosynthesis for enhanced subsurface oxygen delivery.

PubMed

Lanzarini-Lopes, Mariana; Delgado, Anca G; Guo, Yuanming; Dahlen, Paul; Westerhoff, Paul

2018-03-01

Remediation of polluted groundwater often requires oxygen delivery into subsurface to sustain aerobic bacteria. Air sparging or injection of oxygen containing solutions (e.g., hydrogen peroxide) into the subsurface are common. In this study visible light was delivered into the subsurface using radially emitting optical fibers. Phototrophic organisms grew near the optical fiber in a saturated sand column. When applying light in on-off cycles, dissolved oxygen (DO) varied from super saturation levels of >15 mg DO/L in presence of light to under-saturation (<5 mg DO/L) in absence of light. Non-photosynthetic bacteria dominated at longer radial distances from the fiber, presumably supported by soluble microbial products produced by the photosynthetic microorganisms. The dissolved oxygen variations alter redox condition changes in response to light demonstrate the potential to biologically deliver oxygen into the subsurface and support a diverse microbial community. The ability to deliver oxygen and modulate redox conditions on diurnal cycles using solar light may provide a sustainable, long term strategy for increasing dissolved oxygen levels in subsurface environments and maintaining diverse biological communities. Copyright © 2017 Elsevier Ltd. All rights reserved.

A comparative study of the mechanical behaviour of thermally oxidised commercially pure titanium and zirconium.

PubMed

Alansari, A; Sun, Y

2017-10-01

The objective of this study is to compare the mechanical behaviour of thermally oxidised commercially pure titanium (CP-Ti) and commercially pure zirconium (CP-Zr). For this purpose, these two bio-metals were thermally oxidised under the same condition (650°C for 6h) and the oxidised specimens were characterised using various analytical and experimental techniques, including oxygen uptake analysis, layer thickness and hardness measurements, scratch tests, dry sliding friction and wear tests and tribocorrosion tests in Ringer's solution. The results show that under the present thermal oxidation condition, 4 times more oxygen is introduced into CP-Zr than into CP-Ti and the oxide layer produced on CP-Zr is nearly 6 times thicker than that on CP-Ti. Thermally oxidised CP-Zr possesses a higher hardness, a deeper hardening depth and better scratch resistance than thermally oxidised CP-Ti. Under dry sliding and tribocorrosion conditions, thermally oxidised CP-Zr also possesses much better resistance to material removal and a higher load bearing capacity than thermally oxidised CP-Ti. Thus, thermally oxidised Zr possesses much better mechanical behaviour than thermally oxidised Ti. Copyright © 2017 Elsevier Ltd. All rights reserved.

Atomic layer deposition of zirconium silicate films using zirconium tetrachloride and tetra-n-butyl orthosilicate

NASA Astrophysics Data System (ADS)

Kim, Won-Kyu; Kang, Sang-Woo; Rhee, Shi-Woo; Lee, Nae-In; Lee, Jong-Ho; Kang, Ho-Kyu

2002-11-01

Atomic layer chemical vapor deposition of zirconium silicate films with a precursor combination of ZrCl4 and tetra-n-butyl orthosilicate (TBOS) was studied for high dielectric gate insulators. The effect of deposition conditions, such as deposition temperature, pulse time for purge and precursor injection on the deposition rate per cycle, and composition of the film were studied. At 400 °C, the growth rate saturated to 1.35 Å/cycle above 500 sccm of the argon purge flow rate. The growth rate, composition ratio ((Zr/Zr+Si)), and impurity contents (carbon and chlorine) saturated with the increase of the injection time of ZrCl4 and TBOS and decreased with the increased deposition temperature from 300 to 500 °C. The growth rate, composition ratio, carbon, and chlorine contents of the Zr silicate thin films deposited at 500 °C were 1.05 Å/cycle, 0.23, 1.1 at. %, and 2.1 at. %, respectively. It appeared that by using only zirconium chloride and silicon alkoxide sources, the content of carbon and chlorine impurities could not be lowered below 1%. It was also found that the incorporation rate of metal from halide source was lower than alkoxide source.

Human biokinetic data and a new compartmental model of zirconium--a tracer study with enriched stable isotopes.

PubMed

Greiter, Matthias B; Giussani, Augusto; Höllriegl, Vera; Li, Wei Bo; Oeh, Uwe

2011-09-01

Biokinetic models describing the uptake, distribution and excretion of trace elements are an essential tool in nutrition, toxicology, or internal dosimetry of radionuclides. Zirconium, especially its radioisotope (95)Zr, is relevant to radiation protection due to its production in uranium fission and neutron activation of nuclear fuel cladding material. We present a comprehensive set of human data from a tracer study with stable isotopes of zirconium. The data are used to refine a biokinetic model of zirconium. Six female and seven male healthy adult volunteers participated in the study. It includes 16 complete double tracer investigations with oral ingestion and intravenous injection, and seven supplemental investigations. Tracer concentrations were measured in blood plasma and urine collected up to 100 d after tracer administration. The four data sets (two chemical tracer forms in plasma and urine) each encompass 105-240 measured concentration values above detection limits. Total fractional absorption of ingested zirconium was found to be 0.001 for zirconium in citrate-buffered drinking solution and 0.007 for zirconium oxalate solution. Biokinetic models were developed based on the linear first-order kinetic compartmental model approach used by the International Commission on Radiological Protection (ICRP). The main differences of the optimized systemic model of zirconium to the current ICRP model are (1) recycling into the transfer compartment made necessary by the observed tracer clearance from plasma, (2) different parameters related to fractional absorption for each form of the ingested tracer, and (3) a physiologically based excretion pathway to urine. The study considerably expands the knowledge on the biokinetics of zirconium, which was until now dominated by data from animal studies. The proposed systemic model improves the existing ICRP model, yet is based on the same principles and fits well into the ICRP radiation protection approach. Copyright © 2011

pH-responsive drug delivery system based on AIE luminogen functionalized layered zirconium phosphate nano-platelets

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

Li, Dongdong, E-mail: lidongdong@jlu.edu.cn; Zhang, Yuping; Zhou, Bingbing

2015-05-15

Aggregation-induced emission (AIE) luminogen, quaternary tetraphenylethene cation (TPEN), was successfully incorporated into layered α-zirconium phosphate (α-ZrP) by using co-precipitation method to form inorganic–organic hybrid materials. The obtained materials show the characteristic hexagonal platelet shape with the interlayer distance did not reveal significant difference compared with pure α-ZrP. In addition, the obtained hybrid materials emit strong blue emission centered at 476 nm in aqueous media due to the electrostatic interactions of TPEN with the anionic framework of α-ZrP, which largely restrict their intramolecular rotation. More importantly, the materials provide a pH dependent release of doxorubicin (DOX), suggesting that AIE luminogen functionalizedmore » α-ZrP may be used as an imaging guided and pH-responsive delivery system for targeting therapy. - Graphical abstract: AIE luminogen was successfully incorporated into layered α-zirconium phosphate by a co-precipitation method to form inorganic–organic hybrid materials, showing a pH dependent release of DOX. - Highlights: • AIE luminogen cation was incorporated into layered α-ZrP by co-precipitation method. • The obtained material emits strong blue emission upon UV irradiation. • The material exhibits pH dependent release of DOX. • The AIE functionalized α-ZrP has potential applications in imaging guided therapy.« less

Ornithine Decarboxylase-Mediated Production of Putrescine Influences Ganoderic Acid Biosynthesis by Regulating Reactive Oxygen Species in Ganoderma lucidum

PubMed Central

Wu, Chen-Gao; Tian, Jia-Long; Liu, Rui; Cao, Peng-Fei; Zhang, Tian-Jun; Ren, Ang; Shi, Liang

2017-01-01

ABSTRACT Putrescine is an important polyamine that participates in a variety of stress responses. Ornithine decarboxylase (ODC) is a key enzyme that catalyzes the biosynthesis of putrescine. A homolog of the gene encoding ODC was cloned from Ganoderma lucidum. In the ODC-silenced strains, the transcript levels of the ODC gene and the putrescine content were significantly decreased. The ODC-silenced strains were more sensitive to oxidative stress. The content of ganoderic acid was increased by approximately 43 to 46% in the ODC-silenced strains. The content of ganoderic acid could be recovered after the addition of exogenous putrescine. Additionally, the content of reactive oxygen species (ROS) was significantly increased by approximately 1.3-fold in the ODC-silenced strains. The ROS content was significantly reduced after the addition of exogenous putrescine. The gene transcript levels and the activities of four major antioxidant enzymes were measured to further explore the effect of putrescine on the intracellular ROS levels. Further studies showed that the effect of the ODC-mediated production of putrescine on ROS might be a factor influencing the biosynthesis of ganoderic acid. Our study reports the role of putrescine in large basidiomycetes, providing a basis for future studies of the physiological functions of putrescine in microbes. IMPORTANCE It is well known that ODC and the ODC-mediated production of putrescine play an important role in resisting various environmental stresses, but there are few reports regarding the mechanisms underlying the effect of putrescine on secondary metabolism in microorganisms, particularly in fungi. G. lucidum is gradually becoming a model organism for studying environmental regulation and metabolism. In this study, a homolog of the gene encoding ODC was cloned in Ganoderma lucidum. We found that the transcript level of the ODC gene and the content of putrescine were significantly decreased in the ODC-silenced strains. The

Influence of the chemical and electronic structure on the electrical behavior of zirconium oxynitride films

NASA Astrophysics Data System (ADS)

Carvalho, P.; Chappé, J. M.; Cunha, L.; Lanceros-Méndez, S.; Alpuim, P.; Vaz, F.; Alves, E.; Rousselot, C.; Espinós, J. P.; González-Elipe, A. R.

2008-05-01

This work is devoted to the investigation of decorative zirconium oxynitride, ZrOxNy, films prepared by dc reactive magnetron sputtering, using a 17:3 nitrogen-to-oxygen-ratio gas mixture. The color of the films changed from metallic-like, very bright yellow pale, and golden yellow, for low gas mixture flows [from 0 to about 9SCCM (SCCM denotes cubic centimeter per minute at STP)] to red brownish for intermediate gas flows (values up to 12SCCM). Associated to this color change there is a significant decrease of brightness. With further increase of the reactive gas flow, the color of the samples changed from red brownish to dark blue (samples prepared with 13 and 14SCCM). The films deposited with gas flows above 14SCCM showed only apparent colorations due to interference effects. This change in optical behavior from opaque to transparent (characteristic of a transition from metallic to insulating-type materials), promoted by the change in gas flow values, revealed that significant changes were occurring in the film structure and electronic properties, thus opening new potential applications for the films, beyond those of purely decorative ones. Taking this into account, the electrical behavior of the films was investigated as a function of the reactive gas flow and correlated with the observed chemical, electronic, and structural features. The variations in composition disclosed the existence of four different zones, which were correlated to different crystalline structures. For the so-called zone I, x-ray diffraction revealed the development of films with a B1 NaCl face-centered cubic zirconium nitride-type phase, with some texture changes. Increasing the reactive gas flow, the structure of the films is that of a poorly crystallized overstoichiometric nitride phase, which may be similar to that of Zr3N4, but with some probable oxygen inclusions within nitrogen positions. This region was characterized as zone II. Zone III was indexed as an oxynitride-type phase

Monitoring bisphosphonate surface functionalization and acid stability of hierarchically porous titanium zirconium oxides.

PubMed

Ide, Andreas; Drisko, Glenna L; Scales, Nicholas; Luca, Vittorio; Schiesser, Carl H; Caruso, Rachel A

2011-11-01

To take advantage of the full potential of functionalized transition metal oxides, a well-understood nonsilane based grafting technique is required. The functionalization of mixed titanium zirconium oxides was studied in detail using a bisphosphonic acid, featuring two phosphonic acid groups with high surface affinity. The bisphosphonic acid employed was coupled to a UV active benzamide moiety in order to track the progress of the surface functionalization in situ. Using different material compositions, altering the pH environment, and looking at various annealing conditions, key features of the functionalization process were identified that consequently will allow for intelligent material design. Loading with bisphosphonic acid was highest on supports calcined at 650 °C compared to lower calcination temperatures: A maximum capacity of 0.13 mmol g(-1) was obtained and the adsorption process could be modeled with a pseudo-second-order rate relationship. Heating at 650 °C resulted in a phase transition of the mixed binary oxide to a ternary oxide, titanium zirconium oxide in the srilankite phase. This phase transition was crucial in order to achieve high loading of the bisphosphonic acid and enhanced chemical stability in highly acidic solutions. Due to the inert nature of phosphorus-oxygen-metal bonds, materials functionalized by bisphosphonic acids showed increased chemical stability compared to their nonfunctionalized counterparts in harshly acidic solutions. Leaching studies showed that the acid stability of the functionalized material was improved with a partially crystalline srilankite phase. The materials were characterized using nitrogen sorption, X-ray powder diffraction, and UV-vis spectroscopy; X-ray photoelectron spectroscopy was used to study surface coverage with the bisphosphonic acid molecules.

Elaboration of copper-oxygen mediated C-H activation chemistry in consideration of future fuel and feedstock generation.

PubMed

Lee, Jung Yoon; Karlin, Kenneth D

2015-04-01

To contribute solutions to current energy concerns, improvements in the efficiency of dioxygen mediated C-H bond cleavage chemistry, for example, selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, potentially affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Process for massively hydriding zirconium--uranium fuel elements

DOEpatents

Katz, N.H.

1973-12-01

A method is described of hydriding uranium-zirconium alloy by heating the alloy in a vacuum, introducing hydrogen and maintaining an elevated temperature until occurrence of the beta--delta phase transformation and isobarically cooling the composition. (Official Gazette)

Zirconium-modified materials for selective adsorption and removal of aqueous arsenic

DOEpatents

Zhao, Hongting; Moore, Robert C.

2004-11-30

A method, composition, and apparatus for removing contaminant species from an aqueous medium comprising: providing a material to which zirconium has been added, the material selected from one or more of zeolites, cation-exchangeable clay minerals, fly ash, mesostructured materials, activated carbons, cellulose acetate, and like porous and/or fibrous materials; and contacting the aqueous medium with the material to which zirconium has been added. The invention operates on all arsenic species in the form of arsenate, arsenite and organometallic arsenic, with no pretreatment necessary (e.g., oxidative conversion of arsenite to arsenate).

Preparation of lead-zirconium-titanium film and powder by electrodeposition

DOEpatents

Bhattacharya, R.N.; Ginley, D.S.

1995-10-31

A process is disclosed for the preparation of lead-zirconium-titanium (PZT) film and powder compositions. The process comprises the steps of providing an electrodeposition bath, providing soluble salts of lead, zirconium and titanium metals to this bath, electrically energizing the bath to thereby direct ions of each respective metal to a substrate electrode and cause formation of metallic particles as a recoverable film of PZT powder on the electrode, and also recovering the resultant film as a powder. Recovery of the PZT powder can be accomplished by continually energizing the bath to thereby cause powder initially deposited on the substrate-electrode to drop therefrom into the bath from which it is subsequently removed. A second recovery alternative comprises energizing the bath for a period of time sufficient to cause PZT powder deposition on the substrate-electrode only, from which it is subsequently recovered. PZT film and powder so produced can be employed directly in electronic applications, or the film and powder can be subsequently oxidized as by an annealing process to thereby produce lead-zirconium-titanium oxide for use in electronic applications. 4 figs.

Selective separation of zirconium from uranium in carbonate solutions by ion flotation

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

Jdid, E.A.; Blazy, P.; Mahamadou, A.

1990-05-01

Separation of zirconium from uranium in carbonate media was undertaken by ion flotation. The collector chosen was octylhydroxamic acid (HOHX). It gave a well-flocculated precipitate with zirconium which floated in less than 5 min. The stoichiometry of the reaction is HOHX/Zr = 3.9/1, and the selectivity in the presence of uranium is very high. In fact, for a ratio {Phi} = (HOHX),M/(Zr),M, which is just stoichiometric and is close to 4, the zirconium removal rate reaches 99%, even in industrial media. The loss of uranium is only 0.5% although its concentration is 37.4 g/L. Mechanisms of separation are not affectedmore » by a variation of pH between 6.7 and 9.8, of temperature up to 60{degree}C, and of carbonate concentration within the 15 to 60 g/L Na{sub 2}CO{sub 3} range.« less

Electrical characteristics of paraelectric lead lanthanum zirconium titanate thin films for dynamic random access memory applications

NASA Astrophysics Data System (ADS)

Jones, R. E., Jr.; Maniar, P. D.; Olowolafe, J. O.; Campbell, A. C.; Mogab, C. J.

1992-02-01

Paraelectric lead lanthanum zirconium titanate (PLZT) films, 150 nm thick, were deposited using a spin-coat, sol-gel process followed by a 650 °C oxygen anneal. X-ray diffraction indicated complete conversion to the perovskite phase. Sputter-deposited platinum electrodes were employed with the PLZT films to form thin-film capacitors with the best combination of high charge storage density (26.1 μC/cm2 at 3 V and 36.4 μC/cm2 at 5 V) and leakage current density (0.2 μA/cm2 at 3 V and 0.5 μA/cm2 at 5 V ) reported to date. The electrical characteristics of these thin-film capacitors meet the requirements for a planar bit cell capacitor for 64-Mbit dynamic random access memories.

Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling☆

PubMed Central

Riethmüller, Michaela; Burger, Nils; Bauer, Georg

2015-01-01

Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2.) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8, followed by caspase-8-mediated enhancement of NOX activity. The biochemical mechanisms described here might be considered as promising principle for the development of novel approaches in tumor therapy that specifically direct membrane-associated catalase of tumor cells and thus utilize tumor cell-specific apoptosis-inducing ROS signaling. PMID:26225731

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties

NASA Astrophysics Data System (ADS)

Marcellini, Moreno; Fernandes, Francisco M.; Dedovets, Dmytro; Deville, Sylvain

2017-04-01

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties.

PubMed

Marcellini, Moreno; Fernandes, Francisco M; Dedovets, Dmytro; Deville, Sylvain

2017-04-14

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Abstraction and art.

PubMed

Gortais, Bernard

2003-07-29

In a given social context, artistic creation comprises a set of processes, which relate to the activity of the artist and the activity of the spectator. Through these processes we see and understand that the world is vaster than it is said to be. Artistic processes are mediated experiences that open up the world. A successful work of art expresses a reality beyond actual reality: it suggests an unknown world using the means and the signs of the known world. Artistic practices incorporate the means of creation developed by science and technology and change forms as they change. Artists and the public follow different processes of abstraction at different levels, in the definition of the means of creation, of representation and of perception of a work of art. This paper examines how the processes of abstraction are used within the framework of the visual arts and abstract painting, which appeared during a period of growing importance for the processes of abstraction in science and technology, at the beginning of the twentieth century. The development of digital platforms and new man-machine interfaces allow multimedia creations. This is performed under the constraint of phases of multidisciplinary conceptualization using generic representation languages, which tend to abolish traditional frontiers between the arts: visual arts, drama, dance and music.

Effect of zirconium nitride physical vapor deposition coating on preosteoblast cell adhesion and proliferation onto titanium screws.

PubMed

Rizzi, Manuela; Gatti, Giorgio; Migliario, Mario; Marchese, Leonardo; Rocchetti, Vincenzo; Renò, Filippo

2014-11-01

Titanium has long been used to produce dental implants. Problems related to its manufacturing, casting, welding, and ceramic application for dental prostheses still limit its use, which highlights the need for technologic improvements. The aim of this in vitro study was to evaluate the biologic performance of titanium dental implants coated with zirconium nitride in a murine preosteoblast cellular model. The purpose of this study was to evaluate the chemical and morphologic characteristics of titanium implants coated with zirconium nitride by means of physical vapor deposition. Chemical and morphologic characterizations were performed by scanning electron microscopy and energy dispersive x-ray spectroscopy, and the bioactivity of the implants was evaluated by cell-counting experiments. Scanning electron microscopy and energy dispersive x-ray spectroscopy analysis found that physical vapor deposition was effective in covering titanium surfaces with zirconium nitride. Murine MC-3T3 preosteoblasts were seeded onto titanium-coated and zirconium nitride-coated screws to evaluate their adhesion and proliferation. These experiments found a significantly higher number of cells adhering and spreading onto zirconium nitride-coated surfaces (P<.05) after 24 hours; after 7 days, both titanium and zirconium nitride surfaces were completely covered with MC-3T3 cells. Analysis of these data indicates that the proposed zirconium nitride coating of titanium implants could make the surface of the titanium more bioactive than uncoated titanium surfaces. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts.

PubMed

Jadhav, Dipak A; Deshpande, Parag A; Ghangrekar, Makarand M

2017-08-01

Application of ZrO 2 , MnO 2 , palladium, palladium-substituted-zirconium oxide (Zr 0.98 Pd 0.02 O 2 ) and palladium-substituted-manganese oxide (Mn 0.98 Pd 0.02 O 2 ) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m 3 ) was achieved in MFC with Mn 0.98 Pd 0.02 O 2 catalyst, which was higher than that with MnO 2 (0.58W/m 3 ) alone; whereas, MFC having Zr 0.98 Pd 0.02 O 2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m 3 , respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO 2 with 20A/m 3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO 2 or ZrO 2 . Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

N-acetylcysteine attenuates reactive-oxygen-species-mediated endoplasmic reticulum stress during liver ischemia-reperfusion injury

PubMed Central

Sun, Yong; Pu, Li-Yong; Lu, Ling; Wang, Xue-Hao; Zhang, Feng; Rao, Jian-Hua

2014-01-01

AIM: To investigate the effects of N-acetylcysteine (NAC) on endoplasmic reticulum (ER) stress and tissue injury during liver ischemia reperfusion injury (IRI). METHODS: Mice were injected with NAC (300 mg/kg) intraperitoneally 2 h before ischemia. Real-time polymerase chain reaction and western blotting determined ER stress molecules (GRP78, ATF4 and CHOP). To analyze the role of NAC in reactive oxygen species (ROS)-mediated ER stress and apoptosis, lactate dehydrogenase (LDH) was examined in cultured hepatocytes treated by H2O2 or thapsigargin (TG). RESULTS: NAC treatment significantly reduced the level of ROS and attenuated ROS-induced liver injury after IRI, based on glutathione, malondialdehyde, serum alanine aminotransferase levels, and histopathology. ROS-mediated ER stress was significantly inhibited in NAC-treated mice. In addition, NAC treatment significantly reduced caspase-3 activity and apoptosis after reperfusion, which correlated with the protein expression of Bcl-2 and Bcl-xl. Similarly, NAC treatment significantly inhibited LDH release from hepatocytes treated by H2O2 or TG. CONCLUSION: This study provides new evidence for the protective effects of NAC treatment on hepatocytes during IRI. Through inhibition of ROS-mediated ER stress, NAC may be critical to inhibit the ER-stress-related apoptosis pathway. PMID:25386077

Cryogenic foam insulation: Abstracted publications

NASA Technical Reports Server (NTRS)

Williamson, F. R.

1977-01-01

A group of documents were chosen and abstracted which contain information on the properties of foam materials and on the use of foams as thermal insulation at cryogenic temperatures. The properties include thermal properties, mechanical properties, and compatibility properties with oxygen and other cryogenic fluids. Uses of foams include applications as thermal insulation for spacecraft propellant tanks, and for liquefied natural gas storage tanks and pipelines.

Multi-Omic Dynamics Associate Oxygenic Photosynthesis with Nitrogenase-Mediated H2 Production in Cyanothece sp. ATCC 51142.

PubMed

Bernstein, Hans C; Charania, Moiz A; McClure, Ryan S; Sadler, Natalie C; Melnicki, Matthew R; Hill, Eric A; Markillie, Lye Meng; Nicora, Carrie D; Wright, Aaron T; Romine, Margaret F; Beliaev, Alexander S

2015-11-03

To date, the proposed mechanisms of nitrogenase-driven photosynthetic H2 production by the diazotrophic unicellular cyanobacterium Cyanothece sp. ATCC 51142 have assumed that reductant and ATP requirements are derived solely from glycogen oxidation and cyclic-electron flow around photosystem I. Through genome-scale transcript and protein profiling, this study presents and tests a new hypothesis on the metabolic relationship between oxygenic photosynthesis and nitrogenase-mediated H2 production in Cyanothece 51142. Our results show that net-positive rates of oxygenic photosynthesis and increased expression of photosystem II reaction centers correspond and are synchronized with nitrogenase expression and H2 production. These findings provide a new and more complete view on the metabolic processes contributing to the energy budget of photosynthetic H2 production and highlight the role of concurrent photocatalytic H2O oxidation as a participating process.

Damage-induced reactive oxygen species regulate vimentin and dynamic collagen-based projections to mediate wound repair

PubMed Central

Freisinger, Chrissy; Rindy, Julie; Golenberg, Netta; Frecentese, Grace; Gibson, Angela; Eliceiri, Kevin W

2018-01-01

Tissue injury leads to early wound-associated reactive oxygen species (ROS) production that mediate tissue regeneration. To identify mechanisms that function downstream of redox signals that modulate regeneration, a vimentin reporter of mesenchymal cells was generated by driving GFP from the vimentin promoter in zebrafish. Early redox signaling mediated vimentin reporter activity at the wound margin. Moreover, both ROS and vimentin were necessary for collagen production and reorganization into projections at the leading edge of the wound. Second harmonic generation time-lapse imaging revealed that the collagen projections were associated with dynamic epithelial extensions at the wound edge during wound repair. Perturbing collagen organization by burn wound disrupted epithelial projections and subsequent wound healing. Taken together our findings suggest that ROS and vimentin integrate early wound signals to orchestrate the formation of collagen-based projections that guide regenerative growth during efficient wound repair. PMID:29336778

Explicit dosimetry for 2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a-mediated photodynamic therapy: macroscopic singlet oxygen modeling.

PubMed

Penjweini, Rozhin; Liu, Baochang; Kim, Michele M; Zhu, Timothy C

2015-01-01

Type II photodynamic therapy (PDT) is based on the photochemical reactions mediated through an interaction between a photosensitizer, ground-state oxygen ([(3)O2]), and light excitation at an appropriate wavelength, which results in production of reactive singlet oxygen ([(1)O2]rx). We use an empirical macroscopic model based on four photochemical parameters for the calculation of [(1)O2]rx threshold concentration ([(1)O2]rx,sh) causing tissue necrosis in tumors after PDT. For this reason, 2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a (HPPH)-mediated PDT was performed interstitially on mice with radiation-induced fibrosarcoma (RIF) tumors. A linear light source at 665 nm with total energy released per unit length of 12 to 100  J/cm and source power per unit length (LS) of 12 to 150  mW/cm was used to induce different radii of necrosis. Then the amount of [(1)O2]rx calculated by the macroscopic model incorporating explicit PDT dosimetry of light fluence distribution, tissue optical properties, and HPPH concentration was correlated to the necrotic radius to obtain the model parameters and [(1)O2]rx,sh. We provide evidence that [(1)O2]rx is a better dosimetric quantity for predicting the treatment outcome than PDT dose, which is proportional to the time integral of the products of the photosensitizer concentration and light fluence rate.

Explicit dosimetry for 2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a-mediated photodynamic therapy: macroscopic singlet oxygen modeling

NASA Astrophysics Data System (ADS)

Penjweini, Rozhin; Liu, Baochang; Kim, Michele M.; Zhu, Timothy C.

2015-12-01

Type II photodynamic therapy (PDT) is based on the photochemical reactions mediated through an interaction between a photosensitizer, ground-state oxygen ([O]), and light excitation at an appropriate wavelength, which results in production of reactive singlet oxygen ([]rx). We use an empirical macroscopic model based on four photochemical parameters for the calculation of []rx threshold concentration ([]rx,sh) causing tissue necrosis in tumors after PDT. For this reason, 2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a (HPPH)-mediated PDT was performed interstitially on mice with radiation-induced fibrosarcoma (RIF) tumors. A linear light source at 665 nm with total energy released per unit length of 12 to 100 J/cm and source power per unit length (LS) of 12 to 150 mW/cm was used to induce different radii of necrosis. Then the amount of []rx calculated by the macroscopic model incorporating explicit PDT dosimetry of light fluence distribution, tissue optical properties, and HPPH concentration was correlated to the necrotic radius to obtain the model parameters and []rx,sh. We provide evidence that []rx is a better dosimetric quantity for predicting the treatment outcome than PDT dose, which is proportional to the time integral of the products of the photosensitizer concentration and light fluence rate.

The effect of environmental factors on selected mechanical properties of zirconium dioxide

NASA Astrophysics Data System (ADS)

Wirwicki, W.; Andrzejewska, A.; Andryszczyk, M.; Siemianowski, P.

2018-04-01

In many centers around the world, research studies are carried out on the mechanical strength of dental materials and glued joints. A literature review shows the variety of testing techniques related to analyzing the strength and durability of the material itself and the glued joints. In dental ceramics, zirconium dioxide is most often used as a base material, and chemically it consists of 97% ZrO2 and 3% Y2O3. This study was to determine the mechanical properties of zirconium dioxide under different environmental conditions. The material is used for the production of dental crowns and tooth bridges in the CAD/CAM technology. This medium is currently one of the most advanced-generation materials used for prosthetic and implant restorations. They were then subjected to a three-point bending test on the Instron ElektroPlus E3000 durability machine. Storage conditions and time have a positive influence on reducing variation in zirconium resistance for active forces and destructive stresses.

Oxygen Modulates the Effectiveness of Granuloma Mediated Host Response to Mycobacterium tuberculosis: A Multiscale Computational Biology Approach

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

Sershen, Cheryl L.; Plimpton, Steven J.; May, Elebeoba E.

Mycobacterium tuberculosis associated granuloma formation can be viewed as a structural immune response that can contain and halt the spread of the pathogen. In several mammalian hosts, including non-human primates, Mtb granulomas are often hypoxic, although this has not been observed in wild type murine infection models. While a presumed consequence, the structural contribution of the granuloma to oxygen limitation and the concomitant impact on Mtb metabolic viability and persistence remains to be fully explored. We develop a multiscale computational model to test to what extent in vivo Mtb granulomas become hypoxic, and investigate the effects of hypoxia on hostmore » immune response efficacy and mycobacterial persistence. Our study integrates a physiological model of oxygen dynamics in the extracellular space of alveolar tissue, an agent-based model of cellular immune response, and a systems biology-based model of Mtb metabolic dynamics. Our theoretical studies suggest that the dynamics of granuloma organization mediates oxygen availability and illustrates the immunological contribution of this structural host response to infection outcome. Furthermore, our integrated model demonstrates the link between structural immune response and mechanistic drivers influencing Mtbs adaptation to its changing microenvironment and the qualitative infection outcome scenarios of clearance, containment, dissemination, and a newly observed theoretical outcome of transient containment. We observed hypoxic regions in the containment granuloma similar in size to granulomas found in mammalian in vivo models of Mtb infection. In the case of the containment outcome, our model uniquely demonstrates that immune response mediated hypoxic conditions help foster the shift down of bacteria through two stages of adaptation similar to thein vitro non-replicating persistence (NRP) observed in the Wayne model of Mtb dormancy. Lastly, the adaptation in part contributes to the ability of Mtb to

Oxygen Modulates the Effectiveness of Granuloma Mediated Host Response to Mycobacterium tuberculosis: A Multiscale Computational Biology Approach

DOE PAGES

Sershen, Cheryl L.; Plimpton, Steven J.; May, Elebeoba E.

2016-02-15

Mycobacterium tuberculosis associated granuloma formation can be viewed as a structural immune response that can contain and halt the spread of the pathogen. In several mammalian hosts, including non-human primates, Mtb granulomas are often hypoxic, although this has not been observed in wild type murine infection models. While a presumed consequence, the structural contribution of the granuloma to oxygen limitation and the concomitant impact on Mtb metabolic viability and persistence remains to be fully explored. We develop a multiscale computational model to test to what extent in vivo Mtb granulomas become hypoxic, and investigate the effects of hypoxia on hostmore » immune response efficacy and mycobacterial persistence. Our study integrates a physiological model of oxygen dynamics in the extracellular space of alveolar tissue, an agent-based model of cellular immune response, and a systems biology-based model of Mtb metabolic dynamics. Our theoretical studies suggest that the dynamics of granuloma organization mediates oxygen availability and illustrates the immunological contribution of this structural host response to infection outcome. Furthermore, our integrated model demonstrates the link between structural immune response and mechanistic drivers influencing Mtbs adaptation to its changing microenvironment and the qualitative infection outcome scenarios of clearance, containment, dissemination, and a newly observed theoretical outcome of transient containment. We observed hypoxic regions in the containment granuloma similar in size to granulomas found in mammalian in vivo models of Mtb infection. In the case of the containment outcome, our model uniquely demonstrates that immune response mediated hypoxic conditions help foster the shift down of bacteria through two stages of adaptation similar to thein vitro non-replicating persistence (NRP) observed in the Wayne model of Mtb dormancy. Lastly, the adaptation in part contributes to the ability of Mtb to

Oxygen Modulates the Effectiveness of Granuloma Mediated Host Response to Mycobacterium tuberculosis: A Multiscale Computational Biology Approach.

PubMed

Sershen, Cheryl L; Plimpton, Steven J; May, Elebeoba E

2016-01-01

Mycobacterium tuberculosis associated granuloma formation can be viewed as a structural immune response that can contain and halt the spread of the pathogen. In several mammalian hosts, including non-human primates, Mtb granulomas are often hypoxic, although this has not been observed in wild type murine infection models. While a presumed consequence, the structural contribution of the granuloma to oxygen limitation and the concomitant impact on Mtb metabolic viability and persistence remains to be fully explored. We develop a multiscale computational model to test to what extent in vivo Mtb granulomas become hypoxic, and investigate the effects of hypoxia on host immune response efficacy and mycobacterial persistence. Our study integrates a physiological model of oxygen dynamics in the extracellular space of alveolar tissue, an agent-based model of cellular immune response, and a systems biology-based model of Mtb metabolic dynamics. Our theoretical studies suggest that the dynamics of granuloma organization mediates oxygen availability and illustrates the immunological contribution of this structural host response to infection outcome. Furthermore, our integrated model demonstrates the link between structural immune response and mechanistic drivers influencing Mtbs adaptation to its changing microenvironment and the qualitative infection outcome scenarios of clearance, containment, dissemination, and a newly observed theoretical outcome of transient containment. We observed hypoxic regions in the containment granuloma similar in size to granulomas found in mammalian in vivo models of Mtb infection. In the case of the containment outcome, our model uniquely demonstrates that immune response mediated hypoxic conditions help foster the shift down of bacteria through two stages of adaptation similar to the in vitro non-replicating persistence (NRP) observed in the Wayne model of Mtb dormancy. The adaptation in part contributes to the ability of Mtb to remain dormant

Oxygen Modulates the Effectiveness of Granuloma Mediated Host Response to Mycobacterium tuberculosis: A Multiscale Computational Biology Approach

PubMed Central

Sershen, Cheryl L.; Plimpton, Steven J.; May, Elebeoba E.

2016-01-01

Mycobacterium tuberculosis associated granuloma formation can be viewed as a structural immune response that can contain and halt the spread of the pathogen. In several mammalian hosts, including non-human primates, Mtb granulomas are often hypoxic, although this has not been observed in wild type murine infection models. While a presumed consequence, the structural contribution of the granuloma to oxygen limitation and the concomitant impact on Mtb metabolic viability and persistence remains to be fully explored. We develop a multiscale computational model to test to what extent in vivo Mtb granulomas become hypoxic, and investigate the effects of hypoxia on host immune response efficacy and mycobacterial persistence. Our study integrates a physiological model of oxygen dynamics in the extracellular space of alveolar tissue, an agent-based model of cellular immune response, and a systems biology-based model of Mtb metabolic dynamics. Our theoretical studies suggest that the dynamics of granuloma organization mediates oxygen availability and illustrates the immunological contribution of this structural host response to infection outcome. Furthermore, our integrated model demonstrates the link between structural immune response and mechanistic drivers influencing Mtbs adaptation to its changing microenvironment and the qualitative infection outcome scenarios of clearance, containment, dissemination, and a newly observed theoretical outcome of transient containment. We observed hypoxic regions in the containment granuloma similar in size to granulomas found in mammalian in vivo models of Mtb infection. In the case of the containment outcome, our model uniquely demonstrates that immune response mediated hypoxic conditions help foster the shift down of bacteria through two stages of adaptation similar to thein vitro non-replicating persistence (NRP) observed in the Wayne model of Mtb dormancy. The adaptation in part contributes to the ability of Mtb to remain dormant

Proteomic analysis reveals diverse proline hydroxylation-mediated oxygen-sensing cellular pathways in cancer cells

PubMed Central

Liu, Bing; Gao, Yankun; Ruan, Hai-Bin; Chen, Yue

2016-01-01

Proline hydroxylation is a critical cellular mechanism regulating oxygen-response pathways in tumor initiation and progression. Yet, its substrate diversity and functions remain largely unknown. Here, we report a system-wide analysis to characterize proline hydroxylation substrates in cancer cells using an immunoaffinity-purification assisted proteomics strategy. We identified 562 sites from 272 proteins in HeLa cells. Bioinformatic analysis revealed that proline hydroxylation substrates are significantly enriched with mRNA processing and stress-response cellular pathways with canonical and diverse flanking sequence motifs. Structural analysis indicates a significant enrichment of proline hydroxylation participating in the secondary structure of substrate proteins. Our study identified and validated Brd4, a key transcription factor, as a novel proline hydroxylation substrate. Functional analysis showed that the inhibition of proline hydroxylation pathway significantly reduced the proline hydroxylation abundance on Brd4 and affected Brd4-mediated transcriptional activity as well as cell proliferation in AML leukemia cells. Taken together, our study identified a broad regulatory role of proline hydroxylation in cellular oxygen-sensing pathways and revealed potentially new targets that dynamically respond to hypoxia microenvironment in tumor cells. PMID:27764789

Reliability and failure modes of implant-supported zirconium-oxide fixed dental prostheses related to veneering techniques

PubMed Central

Baldassarri, Marta; Zhang, Yu; Thompson, Van P.; Rekow, Elizabeth D.; Stappert, Christian F. J.

2011-01-01

Summary Objectives To compare fatigue failure modes and reliability of hand-veneered and over-pressed implant-supported three-unit zirconium-oxide fixed-dental-prostheses(FDPs). Methods Sixty-four custom-made zirconium-oxide abutments (n=32/group) and thirty-two zirconium-oxide FDP-frameworks were CAD/CAM manufactured. Frameworks were veneered with hand-built up or over-pressed porcelain (n=16/group). Step-stress-accelerated-life-testing (SSALT) was performed in water applying a distributed contact load at the buccal cusp-pontic-area. Post failure examinations were carried out using optical (polarized-reflected-light) and scanning electron microscopy (SEM) to visualize crack propagation and failure modes. Reliability was compared using cumulative-damage step-stress analysis (Alta-7-Pro, Reliasoft). Results Crack propagation was observed in the veneering porcelain during fatigue. The majority of zirconium-oxide FDPs demonstrated porcelain chipping as the dominant failure mode. Nevertheless, fracture of the zirconium-oxide frameworks was also observed. Over-pressed FDPs failed earlier at a mean failure load of 696 ± 149 N relative to hand-veneered at 882 ± 61 N (profile I). Weibull-stress-number of cycles-unreliability-curves were generated. The reliability (2-sided at 90% confidence bounds) for a 400N load at 100K cycles indicated values of 0.84 (0.98-0.24) for the hand-veneered FDPs and 0.50 (0.82-0.09) for their over-pressed counterparts. Conclusions Both zirconium-oxide FDP systems were resistant under accelerated-life-time-testing. Over-pressed specimens were more susceptible to fatigue loading with earlier veneer chipping. PMID:21557985

Evaluation of macrocyclic hydroxyisophthalamide ligands as chelators for zirconium-89

PubMed Central

Xu, Jide; Tatum, David; Magda, Darren

2017-01-01

The development of bifunctional chelators (BFCs) for zirconium-89 immuno-PET applications is an area of active research. Herein we report the synthesis and evaluation of octadentate hydroxyisophthalamide ligands (1 and 2) as zirconium-89 chelators. While both radiometal complexes could be prepared quantitatively and with excellent specific activity, preparation of 89Zr-1 required elevated temperature and an increased reaction time. 89Zr-1 was more stable than 89Zr-2 when challenged in vitro by excess DTPA or serum proteins and in vivo during acute biodistribution studies. Differences in radiometal complex stability arise from structural changes between the two ligand systems, and suggest further ligand optimization is necessary to enhance 89Zr chelation. PMID:28575044

Evaluation of macrocyclic hydroxyisophthalamide ligands as chelators for zirconium-89.

PubMed

Bhatt, Nikunj B; Pandya, Darpan N; Xu, Jide; Tatum, David; Magda, Darren; Wadas, Thaddeus J

2017-01-01

The development of bifunctional chelators (BFCs) for zirconium-89 immuno-PET applications is an area of active research. Herein we report the synthesis and evaluation of octadentate hydroxyisophthalamide ligands (1 and 2) as zirconium-89 chelators. While both radiometal complexes could be prepared quantitatively and with excellent specific activity, preparation of 89Zr-1 required elevated temperature and an increased reaction time. 89Zr-1 was more stable than 89Zr-2 when challenged in vitro by excess DTPA or serum proteins and in vivo during acute biodistribution studies. Differences in radiometal complex stability arise from structural changes between the two ligand systems, and suggest further ligand optimization is necessary to enhance 89Zr chelation.

Myosin Activator Omecamtiv Mecarbil Increases Myocardial Oxygen Consumption and Impairs Cardiac Efficiency Mediated by Resting Myosin ATPase Activity.

PubMed

Bakkehaug, Jens Petter; Kildal, Anders Benjamin; Engstad, Erik Torgersen; Boardman, Neoma; Næsheim, Torvind; Rønning, Leif; Aasum, Ellen; Larsen, Terje Steinar; Myrmel, Truls; How, Ole-Jakob

2015-07-01

Omecamtiv mecarbil (OM) is a novel inotropic agent that prolongs systolic ejection time and increases ejection fraction through myosin ATPase activation. We hypothesized that a potentially favorable energetic effect of unloading the left ventricle, and thus reduction of wall stress, could be counteracted by the prolonged contraction time and ATP-consumption. Postischemic left ventricular dysfunction was created by repetitive left coronary occlusions in 7 pigs (7 healthy pigs also included). In both groups, systolic ejection time and ejection fraction increased after OM (0.75 mg/kg loading for 10 minutes, followed by 0.5 mg/kg/min continuous infusion). Cardiac efficiency was assessed by relating myocardial oxygen consumption to the cardiac work indices, stroke work, and pressure-volume area. To circumvent potential neurohumoral reflexes, cardiac efficiency was additionally assessed in ex vivo mouse hearts and isolated myocardial mitochondria. OM impaired cardiac efficiency; there was a 31% and 23% increase in unloaded myocardial oxygen consumption in healthy and postischemic pigs, respectively. Also, the oxygen cost of the contractile function was increased by 63% and 46% in healthy and postischemic pigs, respectively. The increased unloaded myocardial oxygen consumption was confirmed in OM-treated mouse hearts and explained by an increased basal metabolic rate. Adding the myosin ATPase inhibitor, 2,3-butanedione monoxide abolished all surplus myocardial oxygen consumption in the OM-treated hearts. Omecamtiv mecarbil, in a clinically relevant model, led to a significant myocardial oxygen wastage related to both the contractile and noncontractile function. This was mediated by that OM induces a continuous activation in resting myosin ATPase. © 2015 American Heart Association, Inc.

No difference in in vivo polyethylene wear particles between oxidized zirconium and cobalt-chromium femoral component in total knee arthroplasty.

PubMed

Minoda, Yukihide; Hata, Kanako; Iwaki, Hiroyoshi; Ikebuchi, Mitsuhiko; Hashimoto, Yusuke; Inori, Fumiaki; Nakamura, Hiroaki

2014-03-01

Polyethylene wear particle generation is one of the most important factors affecting mid- to long-term results of total knee arthroplasties. Oxidized zirconium was introduced as a material for femoral components to reduce polyethylene wear generation. However, an in vivo advantage of oxidized zirconium on polyethylene wear particle generation is still controversial. The purpose of this study was to compare in vivo polyethylene wear particles between oxidized zirconium total knee prosthesis and conventional cobalt-chromium (Co-Cr) total knee prosthesis. Synovial fluid was obtained from the knees of 6 patients with oxidized zirconium total knee prosthesis and from 6 patients with conventional cobalt-chromium (Co-Cr) total knee prosthesis 12 months after the operation. Polyethylene particles were isolated and examined using a scanning electron microscope and image analyser. Total number of particles in each knee was 3.3 ± 1.3 × 10(7) in the case of oxidized zirconium (mean ± SD) and 3.4 ± 1.2 × 10(7) in that of Co-Cr (n.s.). The particle size (equivalent circle diameter) was 0.8 ± 0.3 μm in the case of oxidized zirconium and 0.6 ± 0.1 μm in that of Co-Cr (n.s.). The particle shape (aspect ratio) was 1.4 ± 0.0 in the case of oxidized zirconium and 1.4 ± 0.0 in that of metal Co-Cr (n.s). Although newly introduced oxidized zirconium femoral component did not reduce the in vivo polyethylene wear particles in early clinical stage, there was no adverse effect of newly introduced material. At this moment, there is no need to abandon oxidized zirconium femoral component. However, further follow-up of polyethylene wear particle generation should be performed to confirm the advantage of the oxidized zirconium femoral component. Therapeutic study, Level III.

Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling.

PubMed

Riethmüller, Michaela; Burger, Nils; Bauer, Georg

2015-12-01

Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2(.)) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8, followed by caspase-8-mediated enhancement of NOX activity. The biochemical mechanisms described here might be considered as promising principle for the development of novel approaches in tumor therapy that specifically direct membrane-associated catalase of tumor cells and thus utilize tumor cell-specific apoptosis-inducing ROS signaling. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Oxygen self-diffusion mechanisms in monoclinic Zr O2 revealed and quantified by density functional theory, random walk analysis, and kinetic Monte Carlo calculations

NASA Astrophysics Data System (ADS)

Yang, Jing; Youssef, Mostafa; Yildiz, Bilge

2018-01-01

In this work, we quantify oxygen self-diffusion in monoclinic-phase zirconium oxide as a function of temperature and oxygen partial pressure. A migration barrier of each type of oxygen defect was obtained by first-principles calculations. Random walk theory was used to quantify the diffusivities of oxygen interstitials by using the calculated migration barriers. Kinetic Monte Carlo simulations were used to calculate diffusivities of oxygen vacancies by distinguishing the threefold- and fourfold-coordinated lattice oxygen. By combining the equilibrium defect concentrations obtained in our previous work together with the herein calculated diffusivity of each defect species, we present the resulting oxygen self-diffusion coefficients and the corresponding atomistically resolved transport mechanisms. The predicted effective migration barriers and diffusion prefactors are in reasonable agreement with the experimentally reported values. This work provides insights into oxygen diffusion engineering in Zr O2 -related devices and parametrization for continuum transport modeling.

Neuroprotective Effects of Reactive Oxygen Species Mediated by BDNF-Independent Activation of TrkB

PubMed Central

Huang, Yang Zhong; McNamara, James O.

2012-01-01

Reactive oxygen species (ROS) have diverse biological consequences in the mammalian CNS, but the molecular targets mediating these pleiotropic effects are incompletely understood. Like ROS, the neurotrophin receptor, TrkB receptor tyrosine kinase, has diverse effects in the developing and mature mammalian brain. Our discovery that zinc can transactivate TrkB, together with the finding that ROS can trigger zinc release from cytosolic zinc binding proteins, led us to hypothesize that ROS can transactivate TrkB in CNS neurons by a zinc-dependent mechanism. We found that both exogenous H2O2 and endogenous ROS activate TrkB signaling by a Src family kinase-dependent but brain-derived neurotrophic factor-independent mechanism in cultured rat cortical neurons. Exogenous H2O2 enhances cytosolic zinc content in a metallothionein-3 (MT-3)-requiring manner. Both exogenous H2O2 and endogenous ROS mediated transactivation of TrkB requires intracellular zinc and MT-3. The ROS-triggered transactivation of TrkB exerts neuroprotective effects, because inhibition of TrkB kinase activity or uncoupling Shc signaling from TrkB exacerbates neuronal cell death induced by H2O2. Thus, we propose a molecular signaling event whereby ROS induce release of zinc from cytosolic MT-3, the increased cytosolic zinc transactivates TrkB, and the enhanced Shc signaling downstream from TrkB promotes prosurvival effects. We suggest that such neuroprotective effects mediated by ROS are operative in diverse acute and chronic neurological disorders. PMID:23115189

The Effect of Luting Cement and Titanium Base on the Final Color of Zirconium Oxide Core Material.

PubMed

Capa, Nuray; Tuncel, Ilkin; Tak, Onjen; Usumez, Aslihan

2017-02-01

To evaluate the effects of different types of luting cements and different colors of zirconium cores on the final color of the restoration that simulates implant-supported fixed partial dentures (FPDs) by using a titanium base on the bottom. One hundred and twenty zirconium oxide core plates (Zr-Zahn; 10 mm in width, 5 mm in length, 0.5 mm in height) were prepared in different shades (n = 20; noncolored, A2, A3, B1, C2, D2). The specimens were subdivided into two subgroups for the two types of luting cements (n = 10). The initial color measurements were made on zirconium oxide core plates using a spectrometer. To create the cement thicknesses, stretch strips with holes in the middle (5 mm in diameter, 70 μm in height) were used. The second measurement was done on the zirconium oxide core plates after the application of the resin cement (U-200, A2 Shade) or polycarboxylate cement (Lumicon). The final measurement was done after placing the titanium discs (5 mm in diameter, 3 mm in height) in the bottom. The data were analyzed with two-way ANOVA and Tukey's honestly significant differences (HSD) tests (α = 0.05). The ∆E* ab value was higher in the resin cement-applied group than in the polycarboxylate cement-applied group (p < 0.001). The highest ∆E* ab value was recorded for the zirconium oxide core-resin cement-titanium base, and the lowest was recorded for the polycarboxylate cement-zirconium oxide core (p < 0.001). The luting cement, the presence of titanium, and the color of zirconium are all important factors that determine the final shade of zirconia cores in implant-supported FPDs. © 2015 by the American College of Prosthodontists.

Mineral resource of the month: zirconium and hafnium

USGS Publications Warehouse

Gambogi, Joseph

2007-01-01

Zirconium and hafnium are corrosion-resistant metals that are grouped in the same family as titanium on the periodic table. The two elements commonly occur in oxide and silicate minerals and have significant economic importance in everything from ink, ceramics and golf shoes to nuclear fuel rods.

A novel ultrasonication method in the preparation of zirconium impregnated cellulose for effective fluoride adsorption.

PubMed

Barathi, M; Kumar, A Santhana Krishna; Rajesh, N

2014-05-01

In the present work, we propose for the first time a novel ultrasound assisted methodology involving the impregnation of zirconium in a cellulose matrix. Fluoride from aqueous solution interacts with the cellulose hydroxyl groups and the cationic zirconium hydroxide. Ultrasonication ensures a green and quick alternative to the conventional time intensive method of preparation. The effectiveness of this process was confirmed by comprehensive characterization of zirconium impregnated cellulose (ZrIC) adsorbent using Fourier transform infrared spectroscopy (FT-IR), energy dispersive X-ray spectrometry (EDX) and X-ray diffraction (XRD) studies. The study of various adsorption isotherm models, kinetics and thermodynamics of the interaction validated the method. Copyright © 2013 Elsevier B.V. All rights reserved.

The Role of Oxygen Sensors, Hydroxylases, and HIF in Cardiac Function and Disease.

PubMed

Townley-Tilson, W H Davin; Pi, Xinchun; Xie, Liang

2015-01-01

Ischemic heart disease is the leading cause of death worldwide. Oxygen-sensing proteins are critical components of the physiological response to hypoxia and reperfusion injury, but the role of oxygen and oxygen-mediated effects is complex in that they can be cardioprotective or deleterious to the cardiac tissue. Over 200 oxygen-sensing proteins mediate the effects of oxygen tension and use oxygen as a substrate for posttranslational modification of other proteins. Hydroxylases are an essential component of these oxygen-sensing proteins. While a major role of hydroxylases is regulating the transcription factor HIF, we investigate the increasing scope of hydroxylase substrates. This review discusses the importance of oxygen-mediated effects in the heart as well as how the field of oxygen-sensing proteins is expanding, providing a more complete picture into how these enzymes play a multifaceted role in cardiac function and disease. We also review how oxygen-sensing proteins and hydroxylase function could prove to be invaluable in drug design and therapeutic targets for heart disease.

Extensive Bone Reaction From Catastrophic Oxidized Zirconium Wear.

PubMed

Cassar-Gheiti, Adrian J; Collins, Dennis; McCarthy, Tom

2016-01-01

The use of alternative bearing surfaces for total hip arthroplasty has become popular to minimize wear and increase longevity, especially in young patients. Oxidized zirconium (Oxinium; Smith & Nephew, Memphis, Tennessee) femoral heads were introduced in the past decade for use in total hip arthroplasty. The advantages of oxidized zirconium include less risk of fracture compared with traditional ceramic heads. This case report describes a patient with a history of bilateral avascular necrosis of the femoral head after chemotherapy for acute lymphoblastic leukemia. Nonoperative management of avascular necrosis failed, and the patient was treated with bilateral total hip arthroplasty. The patient was followed at regular intervals and had slow eccentric polyethylene wear during a 10-year period. After 10 years, the patient had accelerated wear, with femoral and acetabular bone changes as a result of Oxinium and ultrahigh-molecular-weight polyethylene wear during a 6-month period. This article highlights the unusual accelerated bone changes that occurred as a result of Oxinium wear particles. Copyright 2016, SLACK Incorporated.

Abstraction and art.

PubMed Central

Gortais, Bernard

2003-01-01

In a given social context, artistic creation comprises a set of processes, which relate to the activity of the artist and the activity of the spectator. Through these processes we see and understand that the world is vaster than it is said to be. Artistic processes are mediated experiences that open up the world. A successful work of art expresses a reality beyond actual reality: it suggests an unknown world using the means and the signs of the known world. Artistic practices incorporate the means of creation developed by science and technology and change forms as they change. Artists and the public follow different processes of abstraction at different levels, in the definition of the means of creation, of representation and of perception of a work of art. This paper examines how the processes of abstraction are used within the framework of the visual arts and abstract painting, which appeared during a period of growing importance for the processes of abstraction in science and technology, at the beginning of the twentieth century. The development of digital platforms and new man-machine interfaces allow multimedia creations. This is performed under the constraint of phases of multidisciplinary conceptualization using generic representation languages, which tend to abolish traditional frontiers between the arts: visual arts, drama, dance and music. PMID:12903659

Comparison of surface modified zirconia implants with commercially available zirconium and titanium implants: a histological study in pigs.

PubMed

Gredes, Tomasz; Kubasiewicz-Ross, Pawel; Gedrange, Tomasz; Dominiak, Marzena; Kunert-Keil, Christiane

2014-08-01

New biomaterials and their various surface modifications should undergo in vitro and in vivo evaluation before clinical trials. The objective of our in vivo study was to evaluate the biocompatibility of newly created zirconium implant surfaces after implantation in the lower jaw of pigs and compare the osseointegration of these dental implants with commercially available zirconium and titanium implants. After a healing period of 12 weeks, a histological analysis of the soft and hard tissues and a histomorphometric analysis of the bone-implant contact (BIC) were performed. The implant surfaces showed an intimate connection to the adjacent bone for all tested implants. The 3 newly created zirconium implant surfaces achieved a BIC of 45% on average in comparison with a BIC of 56% from the reference zirconium implants and 35% from titanium implants. Furthermore, the new zirconium implants had a better attachment to gingival and bone tissues in the range of implant necks as compared with the reference implants. The results suggest that the new implants comparably osseointegrate within the healing period, and they have a good in vivo biocompatibility.

SEPARATING HAFNIUM FROM ZIRCONIUM

DOEpatents

Lister, B.A.J.; Duncan, J.F.; Hutcheon, J.M.

1956-08-21

Substantially complete separation of zirconium from hafnium may be obtained by elution of ion exchange material, on which compounds of the elements are adsorbed, with an approximately normal solution of sulfuric acid. Preferably the acid concentration is between 0.8 N amd 1.2 N, amd should not exceed 1.5 N;. Increasing the concentration of sulfate ion in the eluting solution by addition of a soluble sulfate, such as sodium sulfate, has been found to be advantageous. The preferred ion exchange materials are sulfonated polystyrene resins such as Dowex 50,'' and are preferably arranged in a column through which the solutions are passed.

Photoactivatable protein labeling by singlet oxygen mediated reactions.

PubMed

To, Tsz-Leung; Medzihradszky, Katalin F; Burlingame, Alma L; DeGrado, William F; Jo, Hyunil; Shu, Xiaokun

2016-07-15

Protein-protein interactions regulate many biological processes. Identification of interacting proteins is thus an important step toward molecular understanding of cell signaling. The aim of this study was to investigate the use of photo-generated singlet oxygen and a small molecule for proximity labeling of interacting proteins in cellular environment. The protein of interest (POI) was fused with a small singlet oxygen photosensitizer (miniSOG), which generates singlet oxygen ((1)O2) upon irradiation. The locally generated singlet oxygen then activated a biotin-conjugated thiol molecule to form a covalent bond with the proteins nearby. The labeled proteins can then be separated and subsequently identified by mass spectrometry. To demonstrate the applicability of this labeling technology, we fused the miniSOG to Skp2, an F-box protein of the SCF ubiquitin ligase, and expressed the fusion protein in mammalian cells and identified that the surface cysteine of its interacting partner Skp1 was labeled by the biotin-thiol molecule. This photoactivatable protein labeling method may find important applications including identification of weak and transient protein-protein interactions in the native cellular context, as well as spatial and temporal control of protein labeling. Copyright © 2016 Elsevier Ltd. All rights reserved.

A comparative study of zirconium and titanium implants in rat: osseointegration and bone material quality.

PubMed

Hoerth, Rebecca M; Katunar, María R; Gomez Sanchez, Andrea; Orellano, Juan C; Ceré, Silvia M; Wagermaier, Wolfgang; Ballarre, Josefina

2014-02-01

Permanent metal implants are widely used in human medical treatments and orthopedics, for example as hip joint replacements. They are commonly made of titanium alloys and beyond the optimization of this established material, it is also essential to explore alternative implant materials in view of improved osseointegration. The aim of our study was to characterize the implant performance of zirconium in comparison to titanium implants. Zirconium implants have been characterized in a previous study concerning material properties and surface characteristics in vitro, such as oxide layer thickness and surface roughness. In the present study, we compare bone material quality around zirconium and titanium implants in terms of osseointegration and therefore characterized bone material properties in a rat model using a multi-method approach. We used light and electron microscopy, micro Raman spectroscopy, micro X-ray fluorescence and X-ray scattering techniques to investigate the osseointegration in terms of compositional and structural properties of the newly formed bone. Regarding the mineralization level, the mineral composition, and the alignment and order of the mineral particles, our results show that the maturity of the newly formed bone after 8 weeks of implantation is already very high. In conclusion, the bone material quality obtained for zirconium implants is at least as good as for titanium. It seems that the zirconium implants can be a good candidate for using as permanent metal prosthesis for orthopedic treatments.

ELECTROLYTIC CLADDING OF ZIRCONIUM ON URANIUM

DOEpatents

Wick, J.J.

1959-09-22

A method is presented for coating uranium with zircoalum by rendering the uranium surface smooth and oxidefree, immersing it in a molten electrolytic bath in NaCI, K/sub 2/ZrF/sub 6/, KF, and ZrO/sub 2/, and before the article reaches temperature equilibrium with the bath, applying an electrolyzing current of 60 amperes per square dectmeter at approximately 3 volts to form a layer of zirconium metal on the uranium.

Hydration characteristics of zirconium oxide replaced Portland cement for use as a root-end filling material.

PubMed

Camilleri, J; Cutajar, A; Mallia, B

2011-08-01

Zirconium oxide can be added to dental materials rendering them sufficiently radiopaque. It can thus be used to replace the bismuth oxide in mineral trioxide aggregate (MTA). Replacement of Portland cement with 30% zirconium oxide mixed at a water/cement ratio of 0.3 resulted in a material with adequate physical properties. This study aimed at investigating the microstructure, pH and leaching in physiological solution of Portland cement replaced zirconium oxide at either water-powder or water-cement ratios of 0.3 for use as a root-end filling material. The hydration characteristics of the materials which exhibited optimal behavior were evaluated. Portland cement replaced by zirconium oxide in varying amounts ranging from 0 to 50% in increments of 10 was prepared and divided into two sets. One set was prepared at a constant water/cement ratio while the other set at a constant water/powder ratio of 0.3. Portland cement and MTA were used as controls. The materials were analyzed under the scanning electron microscope (SEM) and the hydration products were determined. X-ray energy dispersive analysis (EDX) was used to analyze the elemental composition of the hydration products. The pH and the amount of leachate in Hank's balanced salt solution (HBSS) were evaluated. A material that had optimal properties that satisfied set criteria and could replace MTA was selected. The microstructure of the prototype material and Portland cement used as a control was assessed after 30 days using SEM and atomic ratio diagrams of Al/Ca versus Si/Ca and S/Ca versus Al/Ca were plotted. The hydration products of Portland cement replaced with 30% zirconium oxide mixed at water/cement ratio of 0.3 were calcium silicate hydrate, calcium hydroxide and minimal amounts of ettringite and monosulphate. The calcium hydroxide leached in HBSS solution resulted in an increase in the pH value. The zirconium oxide acted as inert filler and exhibited no reaction with the hydration by-products of Portland

Evaluation of macrocyclic hydroxyisophthalamide ligands as chelators for zirconium-89

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

Bhatt, Nikunj B.; Pandya, Darpan N.; Xu, Jide

The development of bifunctional chelators (BFCs) for zirconium-89 immuno-PET applications is an area of active research. We report the synthesis and evaluation of octadentate hydroxyisophthalamide ligands (1 and 2) as zirconium-89 chelators. And while both radiometal complexes could be prepared quantitatively and with excellent specific activity, preparation of 89Zr-1 required elevated temperature and an increased reaction time. 89Zr-1 was more stable than 89Zr-2 when challenged in vitro by excess DTPA or serum proteins and in vivo during acute biodistribution studies. The differences in radiometal complex stability arise from structural changes between the two ligand systems, and suggest further ligand optimizationmore » is necessary to enhance 89Zr chelation.« less

Evaluation of macrocyclic hydroxyisophthalamide ligands as chelators for zirconium-89

DOE PAGES

Bhatt, Nikunj B.; Pandya, Darpan N.; Xu, Jide; ...

2017-06-02

The development of bifunctional chelators (BFCs) for zirconium-89 immuno-PET applications is an area of active research. We report the synthesis and evaluation of octadentate hydroxyisophthalamide ligands (1 and 2) as zirconium-89 chelators. And while both radiometal complexes could be prepared quantitatively and with excellent specific activity, preparation of 89Zr-1 required elevated temperature and an increased reaction time. 89Zr-1 was more stable than 89Zr-2 when challenged in vitro by excess DTPA or serum proteins and in vivo during acute biodistribution studies. The differences in radiometal complex stability arise from structural changes between the two ligand systems, and suggest further ligand optimizationmore » is necessary to enhance 89Zr chelation.« less

ZIRCONIUM-TITANIUM-BERYLLIUM BRAZING ALLOY

DOEpatents

Gilliland, R.G.; Patriarca, P.; Slaughter, G.M.; Williams, L.C.

1962-06-12

A new and improved ternary alloy is described which is of particular utility in braze-bonding parts made of a refractory metal selected from Group IV, V, and VI of the periodic table and alloys containing said metal as a predominating alloying ingredient. The brazing alloy contains, by weight, 40 to 50 per cent zirconium, 40 to 50 per cent titanium, and the balance beryllium in amounts ranging from 1 to 20 per cent, said alloy having a melting point in the range 950 to 1400 deg C. (AEC)

Fracture Mechanisms of Zirconium Diboride Ultra-High Temperature Ceramics under Pulse Loading

NASA Astrophysics Data System (ADS)

Skripnyak, Vladimir V.; Bragov, Anatolii M.; Skripnyak, Vladimir A.; Lomunov, Andrei K.; Skripnyak, Evgeniya G.; Vaganova, Irina K.

2015-06-01

Mechanisms of failure in ultra-high temperature ceramics (UHTC) based on zirconium diboride under pulse loading were studied experimentally by the method of SHPB and theoretically using the multiscale simulation method. The obtained experimental and numerical data are evidence of the quasi-brittle fracture character of nanostructured zirconium diboride ceramics under compression and tension at high strain rates and the room temperatures. Damage of nanostructured porous zirconium diboride -based UHTC can be formed under stress pulse amplitude below the Hugoniot elastic limit. Fracture of nanostructured ultra-high temperature ceramics under pulse and shock-wave loadings is provided by fast processes of intercrystalline brittle fracture and relatively slow processes of quasi-brittle failure via growth and coalescence of microcracks. A decrease of the shear strength can be caused by nano-voids clusters in vicinity of triple junctions between ceramic matrix grains and ultrafine-grained ceramics. This research was supported by grants from ``The Tomsk State University Academic D.I. Mendeleev Fund Program'' and also N. I. Lobachevski State University of Nizhny Novgorod (Grant of post graduate mobility).

Corrosion Behavior of Zirconium Treated Mild Steel with and Without Organic Coating: a Comparative Study

NASA Astrophysics Data System (ADS)

Ghanbari, Alireza; Attar, Mohammadreza Mohammadzade

2014-10-01

In this study, the anti-corrosion performance of phosphated and zirconium treated mild steel (ZTMS) with and without organic coating was evaluated using AC and DC electrochemical techniques. The topography and morphology of the zirconium treated samples were studied using atomic force microscopy (AFM) and field emission scanning electron microscope (FE-SEM) respectively. The results revealed that the anti-corrosion performance of the phosphate layer was superior to the zirconium conversion layer without an organic coating due to very low thickness and porous nature of the ZTMS. Additionally, the corrosion behavior of the organic coated substrates was substantially different. It was found that the corrosion protection performance of the phosphate steel and ZTMS with an organic coating is in the same order.

Colloidal titration of aqueous zirconium solutions with poly(vinyl sulfate) by potentiometric endpoint detection using a toluidine blue selective electrode.

PubMed

Sakurada, Osamu; Kato, Yasutake; Kito, Noriyoshi; Kameyama, Keiichi; Hattori, Toshiaki; Hashiba, Minoru

2004-02-01

Zirconium oxy-salts were hydrolyzed to form positively charged polymer or cluster species in acidic solutions. The zirconium hydrolyzed polymer was found to react with a negatively charged polyelectrolyte, such as poly(vinyl sulfate), and to form a stoichiometric polyion complex. Thus, colloidal titration with poly(vinyl sulfate) was applied to measure the zirconium concentration in an acidic solution by using a Toluidine Blue selective plasticized poly(vinyl chloride) membrane electrode as a potentiometric end-point detecting device. The determination could be performed with 1% of the relative standard deviation. The colloidal titration stoichiometry at pH < or = 2 was one mol of zirconium per equivalent mol of poly(vinyl sulfate).

Significance of Brain Tissue Oxygenation and the Arachidonic Acid Cascade in Stroke

PubMed Central

Rink, Cameron

2011-01-01

Abstract The significance of the hypoxia component of stroke injury is highlighted by hypermetabolic brain tissue enriched with arachidonic acid (AA), a 22:6n-3 polyunsaturated fatty acid. In an ischemic stroke environment in which cerebral blood flow is arrested, oxygen-starved brain tissue initiates the rapid cleavage of AA from the membrane phospholipid bilayer. Once free, AA undergoes both enzyme-independent and enzyme-mediated oxidative metabolism, resulting in the formation of number of biologically active metabolites which themselves contribute to pathological stroke outcomes. This review is intended to examine two divergent roles of molecular dioxygen in brain tissue as (1) a substrate for life-sustaining homeostatic metabolism of glucose and (2) a substrate for pathogenic metabolism of AA under conditions of stroke. Recent developments in research concerning supplemental oxygen therapy as an intervention to correct the hypoxic component of stroke injury are discussed. Antioxid. Redox Signal. 14, 1889–1903. PMID:20673202

The effect of zirconium-based surface treatment on the cathodic disbonding resistance of epoxy coated mild steel

NASA Astrophysics Data System (ADS)

Ghanbari, A.; Attar, M. M.

2014-10-01

The effect of zirconium-based surface treatment on the cathodic disbonding resistance and adhesion performance of an epoxy coated mild steel substrate was investigated. The obtained data from pull-off, cathodic disbonding test and electrochemical impedance spectroscopy (EIS) indicated that the zirconium conversion layer significantly improved the adhesion strength and cathodic disbonding resistance of the epoxy coating. This may be attributed to formation of some polar zirconium compounds on the surface and increment of surface roughness, that were evident in the results of field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM), respectively.

Numerical assessment of bone remodeling around conventionally and early loaded titanium and titanium-zirconium alloy dental implants.

PubMed

Akça, Kıvanç; Eser, Atılım; Çavuşoğlu, Yeliz; Sağırkaya, Elçin; Çehreli, Murat Cavit

2015-05-01

The aim of this study was to investigate conventionally and early loaded titanium and titanium-zirconium alloy implants by three-dimensional finite element stress analysis. Three-dimensional model of a dental implant was created and a thread area was established as a region of interest in trabecular bone to study a localized part of the global model with a refined mesh. The peri-implant tissues around conventionally loaded (model 1) and early loaded (model 2) implants were implemented and were used to explore principal stresses, displacement values, and equivalent strains in the peri-implant region of titanium and titanium-zirconium implants under static load of 300 N with or without 30° inclination applied on top of the abutment surface. Under axial loading, principal stresses in both models were comparable for both implants and models. Under oblique loading, principal stresses around titanium-zirconium implants were slightly higher in both models. Comparable stress magnitudes were observed in both models. The displacement values and equivalent strain amplitudes around both implants and models were similar. Peri-implant bone around titanium and titanium-zirconium implants experiences similar stress magnitudes coupled with intraosseous implant displacement values under conventional loading and early loading simulations. Titanium-zirconium implants have biomechanical outcome comparable to conventional titanium implants under conventional loading and early loading.

Light- and singlet oxygen-mediated antifungal activity of phenylphenalenone phytoalexins.

PubMed

Lazzaro, Alejandra; Corominas, Montserrat; Martí, Cristina; Flors, Cristina; Izquierdo, Laura R; Grillo, Teresa A; Luis, Javier G; Nonell, Santi

2004-07-01

The light-induced singlet oxygen production and antifungal activity of phenylphenalenone phytoalexins isolated from infected banana plants (Musa acuminata) are reported. Upon absorption of light energy all studied phenylphenalenones sensitise the production of singlet oxygen in polar and non-polar media. Antifungal activity of these compounds towards Fusarium oxysporum is enhanced in the presence of light. These results, together with the correlation of IC50 values under illumination with the quantum yield of singlet oxygen production and the enhancing effect of D2O on the antifungal activity, suggest the intermediacy of singlet oxygen produced by electronic excitation of the phenylphenalenone phytoalexins.

Multi-omic dynamics associate oxygenic photosynthesis with nitrogenase-mediated H 2 production in Cyanothece sp. ATCC 51142

DOE PAGES

Bernstein, Hans C.; Charania, Moiz A.; McClure, Ryan S.; ...

2015-11-03

This study combines transcriptomic and proteomic profiling to provide new insights on the metabolic relationship between oxygenic photosynthesis and nitrogenase-mediated H 2 production in the model cyanobacterium, Cyanothece sp. ATCC 51142. To date, the proposed mechanisms used to describe the energy metabolism processes that support H 2 production in Cyanothece 51142 have assumed that ATP and reductant requirements are derived solely from glycogen oxidation and/or cyclic-electron flow around photosystem I. The results from this study present and test an alternative hypothesis by showing that net-positive rates of oxygenic photosynthesis and increased expression of photosystem II reaction centers correspond and aremore » synchronized with nitrogenase expression and H 2 production. These findings provide a new and more complete view on the metabolic processes contributing to the energy budget of photosynthetic H 2 production and highlight the likely role of photocatalytic H 2O oxidation as a major participating process.« less

Process for separation of zirconium-88, rubidium-83 and yttrium-88

DOEpatents

Heaton, Richard C.; Jamriska, Sr., David J.; Taylor, Wayne A.

1994-01-01

A process for selective separation of strontium-82 and strontium-85 from proton irradiated molybdenum targets is provided and includes dissolving the molybdenum target in a hydrogen peroxide solution to form a first ion-containing solution, passing the first ion-containing solution through a first cationic resin whereby ions selected from the group consisting of molybdenum, niobium, technetium, selenium, vanadium, arsenic, germanium, zirconium and rubidium remain in the first ion-containing solution while ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium and zirconium are selectively adsorbed by the first resin, contacting the first resin with an acid solution capable of stripping adsorbed ions from the first cationic exchange resin whereby the adsorbed ions are removed from the first resin to form a second ion-containing solution, evaporating the second ion-containing solution for time sufficient to remove substantially all of the acid and water from the second ion-containing solution whereby a residue remains, dissolving the residue from the evaporated second-ion containing solution in a dilute acid to form a third ion-containing solution, said third ion-containing solution having an acid molarity adapted to permit said ions to be adsorbed by a cationic exchange resin, passing the third ion-containing solution through a second cationic resin whereby the ions are adsorbed by the second resin, contacting the second resin with a dilute sulfuric acid solution whereby the adsorbed ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, and zirconium are selectively removed from the second resin, and contacting the second resin with a dilute acid solution whereby the adsorbed strontium ions are selectively removed. Zirconium, rubidium, and yttrium radioisotopes can also be recovered with additional steps.

Human Chorionic Gonadotropin Mediated Generation of Reactive Oxygen Species Is Sufficient to Induce Meiotic Exit but Not Apoptosis in Rat Oocytes

PubMed Central

Tiwari, Meenakshi; Chaube, Shail K.

2017-01-01

Abstract Generation of reactive oxygen species (ROS) is associated with final stages of follicular development and ovulation in mammals. The human chorionic gonadotropin (hCG) mimics the action of luteinizing hormone and triggers follicular development and ovulation. However, it remains unclear whether hCG induces generation of ROS, if yes, whether hCG-mediated increased level of ROS could induce meiotic exit and/or apoptosis in rat oocytes. For this purpose, cumulus–oocyte complexes (COCs) were collected from ovary of experimental rats injected with 20 IU pregnant mare's serum gonadotropin for 48 h followed by 20 IU hCG for 0, 7, 14, and 21 h. The morphological changes in COCs, meiotic status of oocyte, total ROS, hydrogen peroxide (H2O2), inducible nitric oxide synthase (iNOS), nitric oxide (NO), Bax, Bcl-2, cytochrome c, telomerase reverse transcriptase (TERT) expression levels, and DNA fragmentation were analyzed in COCs. Our data suggest that hCG surge increased total ROS as well as H2O2 levels but decreased iNOS expression and total NO level in oocytes. The hCG-mediated increased level of ROS was sufficient to induce meiotic cell cycle resumption in majority of oocytes as evidenced by meiotic exit from diplotene as well as metaphase-II (M-II) arrest and their meiotic status. However, increase of ROS level due to hCG surge was not sufficient to trigger Bax and cytochrome c expression levels and DNA fragmentation in COCs. In addition, increased TERT activity was observed in oocytes collected 21 h post-hCG surge showing onset of oocyte aging. Taken together, these results suggest that hCG induces generation of ROS sufficient to trigger meiotic exit from diplotene, as well as M-II arrest, but not good enough to induce apoptosis in rat oocytes. PMID:29098117

High-intensity low energy titanium ion implantation into zirconium alloy

NASA Astrophysics Data System (ADS)

Ryabchikov, A. I.; Kashkarov, E. B.; Pushilina, N. S.; Syrtanov, M. S.; Shevelev, A. E.; Korneva, O. S.; Sutygina, A. N.; Lider, A. M.

2018-05-01

This research describes the possibility of ultra-high dose deep titanium ion implantation for surface modification of zirconium alloy Zr-1Nb. The developed method based on repetitively pulsed high intensity low energy titanium ion implantation was used to modify the surface layer. The DC vacuum arc source was used to produce metal plasma. Plasma immersion titanium ions extraction and their ballistic focusing in equipotential space of biased electrode were used to produce high intensity titanium ion beam with the amplitude of 0.5 A at the ion current density 120 and 170 mA/cm2. The solar eclipse effect was used to prevent vacuum arc titanium macroparticles from appearing in the implantation area of Zr sample. Titanium low energy (mean ion energy E = 3 keV) ions were implanted into zirconium alloy with the dose in the range of (5.4-9.56) × 1020 ion/cm2. The effect of ion current density, implantation dose on the phase composition, microstructure and distribution of elements was studied by X-ray diffraction, scanning electron microscopy and glow-discharge optical emission spectroscopy, respectively. The results show the appearance of Zr-Ti intermetallic phases of different stoichiometry after Ti implantation. The intermetallic phases are transformed from both Zr0.7Ti0.3 and Zr0.5Ti0.5 to single Zr0.6Ti0.4 phase with the increase in the implantation dose. The changes in phase composition are attributed to Ti dissolution in zirconium lattice accompanied by the lattice distortions and appearance of macrostrains in intermetallic phases. The depth of Ti penetration into the bulk of Zr increases from 6 to 13 μm with the implantation dose. The hardness and wear resistance of the Ti-implanted zirconium alloy were increased by 1.5 and 1.4 times, respectively. The higher current density (170 mA/cm2) leads to the increase in the grain size and surface roughness negatively affecting the tribological properties of the alloy.

The Contribution of Singlet Oxygen to Insulin Resistance

PubMed Central

2017-01-01

Insulin resistance contributes to the development of diabetes and cardiovascular dysfunctions. Recent studies showed that elevated singlet oxygen-mediated lipid peroxidation precedes and predicts diet-induced insulin resistance (IR), and neutrophils were suggested to be responsible for such singlet oxygen production. This review highlights literature suggesting that insulin-responsive cells such as endothelial cells, hepatocytes, adipocytes, and myocytes also produce singlet oxygen, which contributes to insulin resistance, for example, by generating bioactive aldehydes, inducing endoplasmic reticulum (ER) stress, and modifying mitochondrial DNA. In these cells, nutrient overload leads to the activation of Toll-like receptor 4 and other receptors, leading to the production of both peroxynitrite and hydrogen peroxide, which react to produce singlet oxygen. Cytochrome P450 2E1 and cytochrome c also contribute to singlet oxygen formation in the ER and mitochondria, respectively. Endothelial cell-derived singlet oxygen is suggested to mediate the formation of oxidized low-density lipoprotein which perpetuates IR, partly through neutrophil recruitment to adipose tissue. New singlet oxygen-involving pathways for the formation of IR-inducing bioactive aldehydes such as 4-hydroperoxy-(or hydroxy or oxo)-2-nonenal, malondialdehyde, and cholesterol secosterol A are proposed. Strategies against IR should target the singlet oxygen-producing pathways, singlet oxygen quenching, and singlet oxygen-induced cellular responses. PMID:29081894

The Contribution of Singlet Oxygen to Insulin Resistance.

PubMed

Onyango, Arnold N

2017-01-01

Insulin resistance contributes to the development of diabetes and cardiovascular dysfunctions. Recent studies showed that elevated singlet oxygen-mediated lipid peroxidation precedes and predicts diet-induced insulin resistance (IR), and neutrophils were suggested to be responsible for such singlet oxygen production. This review highlights literature suggesting that insulin-responsive cells such as endothelial cells, hepatocytes, adipocytes, and myocytes also produce singlet oxygen, which contributes to insulin resistance, for example, by generating bioactive aldehydes, inducing endoplasmic reticulum (ER) stress, and modifying mitochondrial DNA. In these cells, nutrient overload leads to the activation of Toll-like receptor 4 and other receptors, leading to the production of both peroxynitrite and hydrogen peroxide, which react to produce singlet oxygen. Cytochrome P450 2E1 and cytochrome c also contribute to singlet oxygen formation in the ER and mitochondria, respectively. Endothelial cell-derived singlet oxygen is suggested to mediate the formation of oxidized low-density lipoprotein which perpetuates IR, partly through neutrophil recruitment to adipose tissue. New singlet oxygen-involving pathways for the formation of IR-inducing bioactive aldehydes such as 4-hydroperoxy-(or hydroxy or oxo)-2-nonenal, malondialdehyde, and cholesterol secosterol A are proposed. Strategies against IR should target the singlet oxygen-producing pathways, singlet oxygen quenching, and singlet oxygen-induced cellular responses.

Lamellar zirconium phosphates to host metals for catalytic purposes.

PubMed

Ballesteros-Plata, Daniel; Infantes-Molina, Antonia; Rodríguez-Aguado, Elena; Braos-García, Pilar; Rodríguez-Castellón, Enrique

2018-02-27

In the present study a porous lamellar zirconium phosphate heterostructure (PPH) formed from zirconium(iv) phosphate expanded with silica galleries (P/Zr molar ratio equal to 2 and (Si + Zr)/P equal to 3) was prepared to host noble metals. Textural and structural characterization of PPH-noble metal materials was carried out in order to elucidate the location and dispersion of the metallic particles and the properties of the resulting material to be used in catalytic processes. In the present paper, their activity in the catalytic hydrodeoxygenation (HDO) reaction of dibenzofuran (DBF) was evaluated. X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) evidenced that the structure of the pillared zirconium phosphate material was not modified by the incorporation of Pt and Pd. Moreover, transmission electron microscopy (TEM) showed a different dispersion of the noble metal. The acidity of the resulting PPH-noble metal materials also changed, although in all cases the acidity was of weak nature, and the incorporation of noble metals affected Brønsted acid sites as observed from 31 P NMR spectra. In general, the textural, structural and acidic properties of the resulting materials suggest that PPH can be considered a good candidate to be used as a catalytic support. Thus, the catalytic results of the PPH-noble metal samples indicated that the Pd sample showed a stable behavior probably ascribed to a high dispersion of the active phase. However, the Pt sample suffered from fast deactivation. The selectivity to the reaction products was strongly dependent on the noble metal employed.

Precision of a CAD/CAM technique for the production of zirconium dioxide copings.

PubMed

Coli, Pierluigi; Karlsson, Stig

2004-01-01

The precision of a computer-aided design/manufacturing (CAD/CAM) system to manufacture zirconium dioxide copings with a predetermined internal space was investigated. Two master models were produced in acrylic resin. One was directly scanned by the Decim Reader. The Decim Producer then manufactured 10 copings from prefabricated zirconium dioxide blocks. Five copings were prepared, aiming for an internal space to the master of 45 microm. The other five copings were prepared for an internal space of 90 microm. The second test model was used to try in the copings produced. The obtained internal space of the ceramic copings was evaluated by separate measurements of the master models and inner surfaces of the copings. The master models were measured at predetermined points with an optical instrument. The zirconium dioxide copings were measured with a contact instrument at the corresponding sites measured in the masters. The first group of copings had a mean internal space to the scanned master of 41 microm and of 53 microm to the try-in master. In general, the internal space along the axial walls of the masters was smaller than that along the occlusal walls. The second group had a mean internal space of 82 microm to the scanned master and of 90 microm to the try-in master. The aimed-for internal space of the copings was achieved by the manufacturer. The CAD/CAM technique tested provided high precision in the manufacture of zirconium dioxide copings.

Evaluation of artifacts generated by zirconium implants in cone-beam computed tomography images.

PubMed

Vasconcelos, Taruska Ventorini; Bechara, Boulos B; McMahan, Clyde Alex; Freitas, Deborah Queiroz; Noujeim, Marcel

2017-02-01

To evaluate zirconium implant artifact production in cone beam computed tomography images obtained with different protocols. One zirconium implant was inserted in an edentulous mandible. Twenty scans were acquired with a ProMax 3D unit (Planmeca Oy, Helsinki, Finland), with acquisition settings ranging from 70 to 90 peak kilovoltage (kVp) and voxel sizes of 0.32 and 0.16 mm. A metal artifact reduction (MAR) tool was activated in half of the scans. An axial slice through the middle region of the implant was selected for each dataset. Gray values (mean ± standard deviation) were measured in two regions of interest, one close to and the other distant from the implant (control area). The contrast-to-noise ratio was also calculated. Standard deviation decreased with greater kVp and when the MAR tool was used. The contrast-to-noise ratio was significantly higher when the MAR tool was turned off, except for low resolution with kVp values above 80. Selection of the MAR tool and greater kVp resulted in an overall reduction of artifacts in images acquired with low resolution. Although zirconium implants do produce image artifacts in cone-bean computed tomography scans, the setting that best controlled artifact generation by zirconium implants was 90 kVp at low resolution and with the MAR tool turned on. Copyright © 2016 Elsevier Inc. All rights reserved.

Weight of Polyethylene Wear Particles is Similar in TKAs with Oxidized Zirconium and Cobalt-chrome Prostheses

PubMed Central

Kim, Jun-Shik; Huh, Wansoo; Lee, Kwang-Hoon

2009-01-01

Background The greater lubricity and resistance to scratching of oxidized zirconium femoral components are expected to result in less polyethylene wear than cobalt-chrome femoral components. Questions/purposes We examined polyethylene wear particles in synovial fluid and compared the weight, size (equivalent circle diameter), and shape (aspect ratio) of polyethylene wear particles in knees with an oxidized zirconium femoral component with those in knees with a cobalt-chrome femoral component. Patients and Methods One hundred patients received an oxidized zirconium femoral component in one knee and a cobalt-chrome femoral component in the other. There were 73 women and 27 men with a mean age of 55.6 years (range, 44–60 years). The minimum followup was 5 years (mean, 5.5 years; range, 5–6 years). Polyethylene wear particles were analyzed using thermogravimetric methods and scanning electron microscopy. Results The weight of polyethylene wear particles produced at the bearing surface was 0.0223 ± 0.0054 g in 1 g synovial fluid in patients with an oxidized zirconium femoral component and 0.0228 ± 0.0062 g in patients with a cobalt-chrome femoral component. Size and shape of polyethylene wear particles were 0.59 ± 0.05 μm and 1.21 ± 0.24, respectively, in the patients with an oxidized zirconium femoral component and 0.52 ± 0.03 μm and 1.27 ± 0.31, respectively, in the patients with a cobalt-chrome femoral component. Knee Society knee and function scores, radiographic results, and complication rate were similar between the knees with an oxidized zirconium and cobalt-chrome femoral component. Conclusions The weight, size, and shape of polyethylene wear particles were similar in the knees with an oxidized zirconium and a cobalt-chrome femoral component. We found the theoretical advantages of this surface did not provide the actual advantage. Level of Evidence Level I, therapeutic study. See the guidelines for Authors for a complete

Enhanced oxygen consumption in Herbaspirillum seropedicae fnr mutants leads to increased NifA mediated transcriptional activation.

PubMed

Batista, Marcelo Bueno; Wassem, Roseli; Pedrosa, Fábio de Oliveira; de Souza, Emanuel Maltempi; Dixon, Ray; Monteiro, Rose Adele

2015-05-07

Orthologous proteins of the Crp/Fnr family have been previously implicated in controlling expression and/or activity of the NifA transcriptional activator in some diazotrophs. This study aimed to address the role of three Fnr-like proteins from H. seropedicae SmR1 in controlling NifA activity and consequent NifA-mediated transcription activation. The activity of NifA-dependent transcriptional fusions (nifA::lacZ and nifB::lacZ) was analysed in a series of H. seropedicae fnr deletion mutant backgrounds. We found that combined deletions in both the fnr1 and fnr3 genes lead to higher expression of both the nifA and nifB genes and also an increased level of nifH transcripts. Expression profiles of nifB under different oxygen concentrations, together with oxygen consumption measurements suggest that the triple fnr mutant has higher respiratory activity when compared to the wild type, which we believe to be responsible for greater stability of the oxygen sensitive NifA protein. This conclusion was further substantiated by measuring the levels of NifA protein and its activity in fnr deletion strains in comparison with the wild-type. Fnr proteins are indirectly involved in controlling the activity of NifA in H. seropedicae, probably as a consequence of their influence on respiratory activity in relation to oxygen availability. Additionally we can suggest that there is some redundancy in the physiological function of the three Fnr paralogs in this organism, since altered respiration and effects on NifA activity are only observed in deletion strains lacking both fnr1 and fnr3.

Efficient UV-emitting X-ray phosphors: octahedral Zr(PO 4) 6 luminescence centers in potassium hafnium-zirconium phosphates K 2Hf 1- xZr x(PO 4) 2 and KHf 2(1- x) Zr 2 x(PO 4) 3

NASA Astrophysics Data System (ADS)

Torardi, C. C.; Miao, C. R.; Li, J.

2003-02-01

Potassium hafnium-zirconium phosphates, K 2Hf 1- xZr x(PO 4) 2 and KHf 2(1- x) Zr 2 x(PO 4) 3, are broad-band UV-emitting phosphors. At room temperature, they have emission peak maxima at approximately 322 and 305 nm, respectively, under 30 kV peak molybdenum X-ray excitation. Both phosphors demonstrate luminescence efficiencies that make them up to ˜60% as bright as commercially available CaWO 4 Hi-Plus. The solid-state and flux synthesis conditions, and X-ray excited UV luminescence of these two phosphors are discussed. Even though the two compounds have different atomic structures, they contain zirconium in the same active luminescence environment as that found in highly efficient UV-emitting BaHf 1- xZr x(PO 4) 2. All the three materials have hafnium and zirconium in octahedral coordination via oxygen-atom corner sharing with six separate PO 4 tetrahedra. This octahedral Zr(PO 4) 6 moiety appears to be an important structural element for efficient X-ray excited luminescence, as are the edge-sharing octahedral TaO 6 chains for tantalate emission.

Theoretical stusy of the reaction between 2,2',4' - trihydroxyazobenzene-5-sulfonic acid and zirconium

USGS Publications Warehouse

Fletcher, Mary H.

1960-01-01

Zirconium reacts with 2,2',4'-trihydroxyazobenzene-5-sulfonic acid in acid solutions to Form two complexes in which the ratios of dye to zirconium are 1 to 1 and 2 to 1. Both complexes are true chelates, with zirconium acting as a bridge between the two orthohydroxy dye groups. Apparent equilibrium constants for the reactions to form each of the complexes are determined. The reactions are used as a basis for the determination of the active component in the dye and a graphical method for the determination of reagent purity is described. Four absorption spectra covering the wave length region from 350 to 750 mu are given, which completely define the color system associated with the reactions in solutions where the hydrochloric acid concentration ranges from 0.0064N to about 7N.

Cobalt porphyrin-mediated oxygen transport in a polymer membrane. Effect of the cobalt porphyrin structure on the oxygen-binding reaction, oxygen-diffusion constants, and oxygen-transport efficiency

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

Nishide, Hiroyuki; Suzuki, Takayuki; Kawakami, Hiroyoshi

1994-05-12

New derivatives of (meso-[alpha],[alpha],[alpha],[alpha]-tetrakis(o-pivalamidophenyl)porphinato)cobalt (CoPs) were characterized by oxygen-binding equilibrium and rate constants of the cobalt centered in the porphyrins. They depended on the structure of the porphyrin; for example, the rate constants of oxygen binding and dissociation (k[sub on] and k[sub off]) for [alpha][sup 3][beta]-CoP[sub 4]P were 3 and 20 times as large as those for [alpha][sup 4]-CoB[sub 4]P, respectively. Oxygen transport through the polymer membranes containing CoPs as the fixed oxygen carriers was facilitated and was affected by the oxygen-binding character or the structure of CoPs. The logarithmically linear correlation of the oxygen-dissociation rate constant of CoPs (k[submore » off] = (3-66) x 10[sup 3] S[sup [minus]1]) with the diffusion constant of oxygen via CoPs fixed in the membranes (D[sub cc] = (3-140) x 10[sup [minus]9] cm[sup 2] s[sup [minus]1]) was given for those six CoP derivatives. 26 refs., 5 figs., 2 tabs.« less

Effect of sodium zirconium cyclosilicate on potassium lowering for 28 days among outpatients with hyperkalemia: the HARMONIZE randomized clinical trial.

PubMed

Kosiborod, Mikhail; Rasmussen, Henrik S; Lavin, Philip; Qunibi, Wajeh Y; Spinowitz, Bruce; Packham, David; Roger, Simon D; Yang, Alex; Lerma, Edgar; Singh, Bhupinder

2014-12-03

Hyperkalemia is a common electrolyte abnormality that may be difficult to manage because of a lack of effective therapies. Sodium zirconium cyclosilicate is a nonabsorbed cation exchanger that selectively binds potassium in the intestine. To evaluate the efficacy and safety of zirconium cyclosilicate for 28 days in patients with hyperkalemia. HARMONIZE was a phase 3, multicenter, randomized, double-blind, placebo-controlled trial evaluating zirconium cyclosilicate in outpatients with hyperkalemia (serum potassium ≥5.1 mEq/L) recruited from 44 sites in the United States, Australia, and South Africa (March-August 2014). Patients (n = 258) received 10 g of zirconium cyclosilicate 3 times daily in the initial 48-hour open-label phase. Patients (n = 237) achieving normokalemia (3.5-5.0 mEq/L) were then randomized to receive zirconium cyclosilicate, 5 g (n = 45 patients), 10 g (n = 51), or 15 g (n = 56), or placebo (n = 85) daily for 28 days. The primary end point was mean serum potassium level in each zirconium cyclosilicate group vs placebo during days 8-29 of the randomized phase. In the open-label phase, serum potassium levels declined from 5.6 mEq/L at baseline to 4.5 mEq/L at 48 hours. Median time to normalization was 2.2 hours, with 84% of patients (95% CI, 79%-88%) achieving normokalemia by 24 hours and 98% (95% CI, 96%-99%) by 48 hours. In the randomized phase, serum potassium was significantly lower during days 8-29 with all 3 zirconium cyclosilicate doses vs placebo (4.8 mEq/L [95% CI, 4.6-4.9], 4.5 mEq/L [95% CI, 4.4-4.6], and 4.4 mEq/L [95% CI, 4.3-4.5] for 5 g, 10 g, and 15 g; 5.1 mEq/L [95% CI, 5.0-5.2] for placebo; P < .001 for all comparisons). The proportion of patients with mean potassium <5.1 mEq/L during days 8-29 was significantly higher in all zirconium cyclosilicate groups vs placebo (36/45 [80%], 45/50 [90%], and 51/54 [94%] for the 5-g, 10-g, and 15-g groups, vs 38/82 [46%] with placebo; P < .001 for each dose

In Situ Enrichment of Phosphopeptides on MALDI Plates Functionalized by Reactive Landing of Zirconium(IV)–n-Propoxide Ions

PubMed Central

Blacken, Grady R.; Volný, Michael; Vaisar, Tomáš; Sadílek, Martin; Tureček, František

2008-01-01

We report substantial in situ enrichment of phosphopeptides in peptide mixtures using zirconium oxide coated plates for detection by MALDI-TOF mass spectrometry. The novel feature of this approach rests on the specific preparation of zirconium oxide coatings using reactive landing on stainless steel support of gas-phase positive ions produced by electrospray of zirconium(IV)–n-propoxide solutions in 1-propanol. Reactive landing was found to produce durable functionalized surfaces for selective phosphopeptide capture and desorption–ionization by MALDI. Enrichment factors on the order of 20–90 were achieved for several monophosphorylated peptides relative to abundant nonphosphorylated peptides in tryptic digests. We demonstrate the ability of the zirconium oxide functionalized MALDI surfaces to facilitate detection of enriched phosphopeptides in mid-femtomole amounts of α-casein digests per MALDI spot. PMID:17569507

SEPARATION OF PLUTONIUM IONS FROM SOLUTION BY ADSORPTION ON ZIRCONIUM PYROPHOSPHATE

DOEpatents

Stoughton, R.W.

1961-01-31

A method is given for separating plutonium in its reduced, phosphate- insoluble state from other substances. It involves contacting a solution containing the plutonium with granular zirconium pyrophosphate.

Microsensor and transcriptomic signatures of oxygen depletion in biofilms associated with chronic wounds: Biofilms and oxygen

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

James, Garth A.; Ge Zhao, Alice; Usui, Marcia

Polymicrobial biofilms have been implicated in delayed wound healing, although the mechanisms by which biofilms impair wound healing are poorly understood. Many species of bacteria produce exotoxins and exoenzymes that may inhibit healing. In addition, oxygen consumption by biofilms may impede wound healing. In this study, we used oxygen microsensors to measure oxygen transects through in vitro-cultured biofilms, biofilms formed in vivo in a diabetic (db/db) mouse model, and ex vivo human chronic wound specimens. The results show that oxygen levels within both euthanized and live mouse wounds had steep gradients that reached minima ranging from 19 to 61% oxygenmore » partial pressure, compared to atmospheric oxygen levels. The oxygen gradients in the mouse wounds were similar to those observed for clinical isolates cultured in vitro and for human ex vivo scabs. No oxygen gradients were observed for heat-killed scabs, suggesting that active metabolism by the viable bacteria contributed to the reduced oxygen partial pressure of the wounds. To characterize the metabolic activities of the bacteria in the mouse wounds, we performed transcriptomics analyses of Pseudomonas aeruginosa biofilms associated with the db/db mice wounds using Affymetrix microarrays. The results demonstrated that the bacteria expressed genes for metabolic activities associated with cell growth. Interestingly, the transcriptome results indicated that the bacteria within the wounds also experienced oxygen-limitation stress. Among the bacterial genes that were expressed in vivo were genes associated with the Anr-mediated hypoxia-stress response. Other bacterial stress response genes highly expressed in vivo were genes associated with stationary-phase growth, osmotic stress, and RpoH-mediated heat shock stress. Overall, the results support the hypothesis that the metabolic activities of bacteria in biofilms act as oxygen sinks in chronic wounds and that the depletion of oxygen contributes to the

Influence of the Oxygen content on the thermal migration of Xenon in ZrCxO1-x

NASA Astrophysics Data System (ADS)

Pipon, Y.; Toulhoat, N.; Moncoffre, N.; Gutierrez, G.; Maître, A.; Gendre, M.

2013-09-01

Zirconium carbide (ZrC) is a refractory ceramic presenting interesting properties such as a high melting point, a very high hardness and a good thermal stability. For these reasons, this material is considered as a candidate for fuel coating for fourth-generation reactors in particular for the Gas cooled Fast Reactors (GFR). The ceramic temperature could reach 1200 °C in normal reactor operation and reach 1700 °C in accidental conditions. It is therefore important to assess the ZrC thermal retention capacity regarding abundant and/or volatile fission products. This paper deals with the behavior of Xenon which is the major gaseous fission product created during fission. Previous studies have shown that Xenon remained motionless in an "Oxygen-poor" matrix such as ZrC0.95O0.05, up to temperatures of 1800 °C. However, Zirconium oxycarbides are known to be very sensitive to oxidation. This study aims therefore at studying the behavior of Xenon in Zirconium oxycarbide samples with different Oxygen contents. Xenon is introduced by ion implantation and the samples are annealed in secondary vacuum in the temperature range 1400 °C-1800 °C. The Oxygen profiles are determined by using the 16O(4He, 4He)16O nuclear reaction at 7.5 MeV and the concentration profiles of Xenon are measured by Rutherford Backscattering Spectrometry at each step of the treatment. The results show that the behavior of the material during annealing with respect to oxidation is strongly related to its initial Oxygen content. More generally, the higher the initial Oxygen content, the more important is the oxidation. Consequently, the Xenon migration is enhanced in Oxygen rich Zirconium carbides. at 1950 °C under vacuum with an applied load of 100 MPa by Spark Plasma Sintering (SPS) at the University of Toulouse (CNRS PNF2 platform) [22]. at 1845 °C under an Ar gas flow with an applied load of 40 MPa by Hot Pressing (HP) at Limoges. Sintered pellets were divided into two batches: (i) a batch of

Reactive oxygen species-mediated therapeutic response and resistance in glioblastoma

PubMed Central

Singer, E; Judkins, J; Salomonis, N; Matlaf, L; Soteropoulos, P; McAllister, S; Soroceanu, L

2015-01-01

Glioblastoma (GBM) resistance to therapy is the most common cause of tumor recurrence, which is ultimately fatal in 90% of the patients 5 years after initial diagnosis. A sub-population of tumor cells with stem-like properties, glioma stem cells (GSCs), is specifically endowed to resist or adapt to the standard therapies, leading to therapeutic resistance. Several anticancer agents, collectively termed redox therapeutics, act by increasing intracellular levels of reactive oxygen species (ROS). In this study, we investigated mechanisms underlying GSC response and resistance to cannabidiol (CBD), a non-toxic, non-psychoactive cannabinoid and redox modulator. Using primary GSCs, we showed that CBD induced a robust increase in ROS, which led to the inhibition of cell survival, phosphorylated (p)-AKT, self-renewal and a significant increase in the survival of GSC-bearing mice. Inhibition of self-renewal was mediated by the activation of the p-p38 pathway and downregulation of key stem cell regulators Sox2, Id1 and p-STAT3. Following CBD treatment, a subset of GSC successfully adapted, leading to tumor regrowth. Microarray, Taqman and functional assays revealed that therapeutic resistance was mediated by enhanced expression of the antioxidant response system Xc catalytic subunit xCT (SLC7A11 (solute carrier family 7 (anionic amino-acid transporter light chain), member 11)) and ROS-dependent upregulation of mesenchymal (MES) markers with concomitant downregulation of proneural (PN) markers, also known as PN–MES transition. This ‘reprogramming' of GSCs occurred in culture and in vivo and was partially due to activation of the NFE2L2 (NRF2 (nuclear factor, erythroid 2-like)) transcriptional network. Using genetic knockdown and pharmacological inhibitors of SLC7A11, we demonstrated that combining CBD treatment with the inhibition of system Xc resulted in synergistic ROS increase leading to robust antitumor effects, that is, decreased GSC survival, self-renewal, and

Fosfomycin enhances phagocyte-mediated killing of Staphylococcus aureus by extracellular traps and reactive oxygen species.

PubMed

Shen, Fengge; Tang, Xudong; Cheng, Wei; Wang, Yang; Wang, Chao; Shi, Xiaochen; An, Yanan; Zhang, Qiaoli; Liu, Mingyuan; Liu, Bo; Yu, Lu

2016-01-18

The successful treatment of bacterial infections is the achievement of a synergy between the host's immune defences and antibiotics. Here, we examined whether fosfomycin (FOM) could improve the bactericidal effect of phagocytes, and investigated the potential mechanisms. FOM enhanced the phagocytosis and extra- or intracellular killing of S. aureus by phagocytes. And FOM enhanced the extracellular killing of S. aureus in macrophage (MФ) and in neutrophils mediated by extracellular traps (ETs). ET production was related to NADPH oxidase-dependent reactive oxygen species (ROS). Additionally, FOM increased the intracellular killing of S. aureus in phagocytes, which was mediated by ROS through the oxidative burst process. Our results also showed that FOM alone induced S. aureus producing hydroxyl radicals in order to kill the bacterial cells in vitro. In a mouse peritonitis model, FOM treatment increased the bactericidal extra- and intracellular activity in vivo, and FOM strengthened ROS and ET production from peritoneal lavage fluid ex vivo. An IVIS imaging system assay further verified the observed in vivo bactericidal effect of the FOM treatment. This work may provide a deeper understanding of the role of the host's immune defences and antibiotic interactions in microbial infections.

Fosfomycin enhances phagocyte-mediated killing of Staphylococcus aureus by extracellular traps and reactive oxygen species

PubMed Central

Shen, Fengge; Tang, Xudong; Cheng, Wei; Wang, Yang; Wang, Chao; Shi, Xiaochen; An, Yanan; Zhang, Qiaoli; Liu, Mingyuan; Liu, Bo; Yu, Lu

2016-01-01

The successful treatment of bacterial infections is the achievement of a synergy between the host’s immune defences and antibiotics. Here, we examined whether fosfomycin (FOM) could improve the bactericidal effect of phagocytes, and investigated the potential mechanisms. FOM enhanced the phagocytosis and extra- or intracellular killing of S. aureus by phagocytes. And FOM enhanced the extracellular killing of S. aureus in macrophage (MФ) and in neutrophils mediated by extracellular traps (ETs). ET production was related to NADPH oxidase-dependent reactive oxygen species (ROS). Additionally, FOM increased the intracellular killing of S. aureus in phagocytes, which was mediated by ROS through the oxidative burst process. Our results also showed that FOM alone induced S. aureus producing hydroxyl radicals in order to kill the bacterial cells in vitro. In a mouse peritonitis model, FOM treatment increased the bactericidal extra- and intracellular activity in vivo, and FOM strengthened ROS and ET production from peritoneal lavage fluid ex vivo. An IVIS imaging system assay further verified the observed in vivo bactericidal effect of the FOM treatment. This work may provide a deeper understanding of the role of the host’s immune defences and antibiotic interactions in microbial infections. PMID:26778774

Zirconium-based conversion film formation on zinc, aluminium and magnesium oxides and their interactions with functionalized molecules

NASA Astrophysics Data System (ADS)

Fockaert, L. I.; Taheri, P.; Abrahami, S. T.; Boelen, B.; Terryn, H.; Mol, J. M. C.

2017-11-01

Zirconium-based conversion treatment of zinc, aluminium and magnesium oxides have been studied in-situ using ATR-FTIR in a Kretschmann geometry. This set-up was coupled to an electrochemical cell, which allowed to obtain chemical and electrochemical information simultaneously as a function of conversion time. This elucidated the strong relation between physico-chemical surface properties and zirconium-based conversion kinetics. Whereas the surface hydroxyl density of zinc and aluminium increased during conversion, magnesium (hydr)oxide was shown to dissolve in the acid solution. Due to this dissolution, strong surface alkalization can be expected, explaining the rapid conversion kinetics. AES depth profiling was used to determine the final oxide thickness and elemental composition. This confirmed that magnesium is most active and forms a zirconium oxide layer approximately 10 times thicker than zinc. On the other hand, the presence of zirconium oxide on aluminium is very low and can be considered as not fully covering the metal oxide. Additionally, the converted oxide chemistry was related to the bonding mechanisms of amide functionalized molecules using ATR-FTIR and XPS. It was shown that inclusion of zirconium altered the acid-base properties, increasing the substrate proton donating capabilities in case of magnesium oxide and increasing hydrogen bonding and Bronsted interactions due to increased surface hydroxide fractions on zinc and aluminium substrates.

Uncovering the Roles of Oxygen in Cr(III) Photoredox Catalysis.

PubMed

Higgins, Robert F; Fatur, Steven M; Shepard, Samuel G; Stevenson, Susan M; Boston, David J; Ferreira, Eric M; Damrauer, Niels H; Rappé, Anthony K; Shores, Matthew P

2016-04-27

A combined experimental and theoretical investigation aims to elucidate the necessary roles of oxygen in photoredox catalysis of radical cation based Diels-Alder cycloadditions mediated by the first-row transition metal complex [Cr(Ph2phen)3](3+), where Ph2phen = bathophenanthroline. We employ a diverse array of techniques, including catalysis screening, electrochemistry, time-resolved spectroscopy, and computational analyses of reaction thermodynamics. Our key finding is that oxygen acts as a renewable energy and electron shuttle following photoexcitation of the Cr(III) catalyst. First, oxygen quenches the excited Cr(3+)* complex; this energy transfer process protects the catalyst from decomposition while preserving a synthetically useful 13 μs excited state and produces singlet oxygen. Second, singlet oxygen returns the reduced catalyst to the Cr(III) ground state, forming superoxide. Third, the superoxide species reduces the Diels-Alder cycloadduct radical cation to the final product and reforms oxygen. We compare the results of these studies with those from cycloadditions mediated by related Ru(II)-containing complexes and find that the distinct reaction pathways are likely part of a unified mechanistic framework where the photophysical and photochemical properties of the catalyst species lead to oxygen-mediated photocatalysis for the Cr-containing complex but radical chain initiation for the Ru congener. These results provide insight into how oxygen can participate as a sustainable reagent in photocatalysis.

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

NASA Astrophysics Data System (ADS)

Romano, Esteban Javier

2005-07-01

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

Aminofluorene-Mediated Biomimetic Domino Amination-Oxygenation of Aldehydes to Amides.

PubMed

Ghosh, Santanu; Jana, Chandan K

2016-11-18

A conceptually novel biomimetic strategy based on a domino amination-oxygenation reaction was developed for direct amidation of aldehydes under metal-free conditions employing molecular oxygen as the oxidant. 9-Aminofluorene derivatives acted as pyridoxamine-5'-phosphate equivalents for efficient, chemoselective, and operationally simple amine-transfer oxygenation reaction. Unprecedented RNH transfer involving secondary amine to produce secondary amides was achieved. In the presence of 18 O 2 , 18 O-amide was formed with excellent (95%) isotopic purity.

Induction of apoptosis by plumbagin through reactive oxygen species-mediated inhibition of topoisomerase II

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

Kawiak, Anna; Piosik, Jacek; Stasilojc, Grzegorz

2007-09-15

Reactive oxygen species (ROS) have been recognized as key molecules, which can selectively modify proteins and therefore regulate cellular signalling including apoptosis. Plumbagin, a naphthoquinone exhibiting antitumor activity, is known to generate ROS and has been found to inhibit the activity of topoisomerase II (Topo II) through the stabilization of the Topo II-DNA cleavable complex. The objective of this research was to clarify the role of ROS and Topo II inhibition in the induction of apoptosis mediated by plumbagin. As determined by the comet assay, plumbagin induced DNA cleavage in HL-60 cells, whereas in a cell line with reduced Topomore » II activity-HL-60/MX2, the level of DNA damage was significantly decreased. The onset of DNA strand break formation in HL-60 cells was delayed in comparison with the generation of intracellular ROS. In HL-60/MX2 cells, ROS were generated at a similar rate, whereas a significant reduction in the level of DNA damage was detected. The pretreatment of cells with N-acetylcysteine (NAC) attenuated plumbagin-induced DNA damage, pointing out to the involvement of ROS generation in cleavable complex formation. These results suggest that plumbagin-induced ROS does not directly damage DNA but requires the involvement of Topo II. Furthermore, experiments carried out using light spectroscopy indicated no direct interactions between plumbagin and DNA. The induction of apoptosis was significantly delayed in HL-60/MX2 cells indicating the involvement of Topo II inhibition in plumbagin-mediated apoptosis. Thus, these findings strongly suggest ROS-mediated inhibition of Topo II as an important mechanism contributing to the apoptosis-inducing properties of plumbagin.« less

Membrane transporters mediating root signalling and adaptive responses to oxygen deprivation and soil flooding.

PubMed

Shabala, Sergey; Shabala, Lana; Barcelo, Juan; Poschenrieder, Charlotte

2014-10-01

This review provides a comprehensive assessment of a previously unexplored topic: elucidating the role that plasma- and organelle-based membrane transporters play in plant-adaptive responses to flooding. We show that energy availability and metabolic shifts under hypoxia and anoxia are critical in regulating membrane-transport activity. We illustrate the high tissue and time dependence of this regulation, reveal the molecular identity of transporters involved and discuss the modes of their regulation. We show that both reduced oxygen availability and accumulation of transition metals in flooded roots result in a reduction in the cytosolic K(+) pool, ultimately determining the cell's fate and transition to programmed cell death (PCD). This process can be strongly affected by hypoxia-induced changes in the amino acid pool profile and, specifically, ϒ-amino butyric acid (GABA) accumulation. It is suggested that GABA plays an important regulatory role, allowing plants to proceed with H2 O2 signalling to activate a cascade of genes that mediate plant adaptation to flooding while at the same time, preventing the cell from entering a 'suicide program'. We conclude that progress in crop breeding for flooding tolerance can only be achieved by pyramiding the numerous physiological traits that confer efficient energy maintenance, cytosolic ion homeostasis, and reactive oxygen species (ROS) control and detoxification. © 2014 John Wiley & Sons Ltd.

Abstracts of NASA-ASRDI publications relevant to aerospace safety research

NASA Technical Reports Server (NTRS)

Mandel, G.; Mckenna, P. J.

1973-01-01

Abstracts covering the following areas are presented: (1) oxygen technology; (2) fire safety; (3) accidents/incidents; (4) toxic spills; (5) aircraft safety; (6) structural failures; (7) nuclear systems; (8) fluid flow; and (9) zero gravity combustion.

Singlet oxygen explicit dosimetry to predict long-term local tumor control for Photofrin-mediated photodynamic therapy

NASA Astrophysics Data System (ADS)

Penjweini, Rozhin; Kim, Michele M.; Ong, Yi Hong; Zhu, Timothy C.

2017-02-01

Although photodynamic therapy (PDT) is an established modality for the treatment of cancer, current dosimetric quantities do not account for the variations in PDT oxygen consumption for different fluence rates (φ). In this study we examine the efficacy of reacted singlet oxygen concentration ([1O2]rx) to predict long-term local control rate (LCR) for Photofrin-mediated PDT. Radiation-induced fibrosarcoma (RIF) tumors in the right shoulders of female C3H mice are treated with different in-air fluences of 225-540 J/cm2 and in-air fluence rate (φair) of 50 and 75 mW/cm2 at 5 mg/kg Photofrin and a drug-light interval of 24 hours using a 1 cm diameter collimated laser beam at 630 nm wavelength. [1O2]rx is calculated by using a macroscopic model based on explicit dosimetry of Photofrin concentration, tissue optical properties, tissue oxygenation and blood flow changes during PDT. The tumor volume of each mouse is tracked for 90 days after PDT and Kaplan-Meier analyses for LCR are performed based on a tumor volume <=100 mm3, for the four dose metrics light fluence, photosensitizer photobleaching rate, PDT dose and [1O2]rx. PDT dose is defined as a temporal integral of photosensitizer concentration and Φ at a 3 mm tumor depth. φ is calculated throughout the treatment volume based on Monte-Carlo simulation and measured tissue optical properties. Our preliminary studies show that [1O2]rx is the best dosimetric quantity that can predict tumor response and correlate with LCR. Moreover, [1O2]rx calculated using the blood flow changes was in agreement with [1O2]rx calculated based on the actual tissue oxygenation.

Electrochemical Cell for Obtaining Oxygen from Carbon Dioxide Atmospheres

NASA Technical Reports Server (NTRS)

Hooker, Matthew; Rast, H. Edward; Rogers, Darren K.; Borja, Luis; Clark, Kevin; Fleming, Kimberly; Mcgurren, Michael; Oldaker, Tom; Sweet, Nanette

1989-01-01

To support human life on the Martian surface, an electrochemical device will be required to obtain oxygen from the carbon dioxide rich atmosphere. The electrolyte employed in such a device must be constructed from extremely thin, dense membranes to efficiently acquire the oxygen necessary to support life. A forming process used industrially in the production of multilayer capacitors and electronic substrates was adapted to form the thin membranes required. The process, known as the tape casting, involves the suspension consisting of solvents and binders. The suspension is passed under a blade, resulting in the production of ceramic membranes between 0.1 and 0.5 mm thick. Once fired, the stabilized zirconia membranes were assembled into the cell design by employing a zirconium phosphate solution as the sealing agent. The resulting ceramic-to-ceramic seals were found to be structurally sound and gas-tight. Furthermore, by using a zirconia-based solution to assemble the cell, the problem of a thermal expansion mismatch was alleviated. By adopting an industrial forming process to produce thin membranes, an electrochemical cell for obtaining oxygen from carbon dioxide was produced. The proposed cell design is unique in that it does not require a complicated manifold system for separating the various gases present in this process, nor does it require a series of complex electrical connections. Thus, the device can reliably obtain the vital oxygen supply from the toxic carbon dioxide atmosphere.

The Effect of Boron and Zirconium on the Structure and Tensile Properties of the Cast Nickel-Based Superalloy ATI 718Plus

NASA Astrophysics Data System (ADS)

Hosseini, Seyed Ali; Abbasi, Seyed Mehdi; Madar, Karim Zangeneh

2018-04-01

The effects of boron and zirconium on cast structure, hardness, and tensile properties of the nickel-based superalloy 718Plus were investigated. For this purpose, five alloys with different contents of boron and zirconium were cast via vacuum induction melting and then purified via vacuum arc remelting. Microstructural analysis by light-optical microscope and scanning electron microscope equipped with energy-dispersive x-ray spectroscopy and phase studies by x-ray diffraction analysis were performed. The results showed that boron and zirconium tend to significantly reduce dendritic arm spacing and increase the amount of Laves, Laves/gamma eutectic, and carbide phases. It was also found that boron led to the formation of B4C and (Cr, Fe, Mo, Ni, Ti)3B2 phases and zirconium led to the formation of intermetallic phases and ZrC carbide. In the presence of boron and zirconium, the hardness and its difference between dendritic branches and inter-dendritic spaces increased by concentrating such phases as Laves in the inter-dendritic spaces. These elements had a negative effect on tensile properties of the alloy, including ductility and strength, mainly because of the increase in the Laves phase. It should be noted that the largest degradation of the tensile properties occurred in the alloys containing the maximum amount of zirconium.

Zirconium Ions Up-Regulate the BMP/SMAD Signaling Pathway and Promote the Proliferation and Differentiation of Human Osteoblasts

PubMed Central

Chen, Yongjuan; Roohani-Esfahani, Seyed-Iman; Lu, ZuFu; Zreiqat, Hala; Dunstan, Colin R.

2015-01-01

Zirconium (Zr) is an element commonly used in dental and orthopedic implants either as zirconia (ZrO2) or in metal alloys. It can also be incorporated into calcium silicate-based ceramics. However, the effects of in vitro culture of human osteoblasts (HOBs) with soluble ionic forms of Zr have not been determined. In this study, primary culture of human osteoblasts was conducted in the presence of medium containing either ZrCl4 or Zirconium (IV) oxynitrate (ZrO(NO3)2) at concentrations of 0, 5, 50 and 500 µM, and osteoblast proliferation, differentiation and calcium deposition were assessed. Incubation of human osteoblast cultures with Zr ions increased the proliferation of human osteoblasts and also gene expression of genetic markers of osteoblast differentiation. In 21 and 28 day cultures, Zr ions at concentrations of 50 and 500 µM increased the deposition of calcium phosphate. In addition, the gene expression of BMP2 and BMP receptors was increased in response to culture with Zr ions and this was associated with increased phosphorylation of SMAD1/5. Moreover, Noggin suppressed osteogenic gene expression in HOBs co-treated with Zr ions. In conclusion, Zr ions appear able to induce both the proliferation and the differentiation of primary human osteoblasts. This is associated with up-regulation of BMP2 expression and activation of BMP signaling suggesting this action is, at least in part, mediated by BMP signaling. PMID:25602473

Induction of Tca8113 tumor cell apoptosis by icotinib is associated with reactive oxygen species mediated p38-MAPK activation.

PubMed

Yang, Cailing; Yan, Jianguo; Yuan, Guoyan; Zhang, Yinghua; Lu, Derong; Ren, Mingxin; Cui, Weigang

2014-08-01

Icotinib, a selective EGFR tyrosine kinase inhibitor (EGFR-TKI), has been shown to exhibit anti-tumor activity against several tumor cell lines. However, the exact molecular mechanism of icotinib's anti-tumor effect remains unknown. This study aims to examine the zytotoxic effect of icotinib on Tca8113 cells and its potential molecular mechanism. Icotinib significantly resulted in dose-dependent cell death as determined by MTT assay, accompanied by increased levels of Bax and DNA fragmentation. Icotinib could also induce Reactive Oxygen Species (ROS) generation. Further studies confirmed that scavenging of reactive oxygen species by N-acetyl-L-cysteine (NAC), and pharmacological inhibition of MAPK reversed icotinib-induced apoptosis in Tca8113 cells. Our data provide evidence that icotinib induces apoptosis, possibly via ROS-mediated MAPK pathway in Tca8113 cells.

Oxygen-glucose deprivation preconditioning protects neurons against oxygen-glucose deprivation/reperfusion induced injury via bone morphogenetic protein-7 mediated ERK, p38 and Smad signalling pathways.

PubMed

Guan, Junhong; Du, Shaonan; Lv, Tao; Qu, Shengtao; Fu, Qiang; Yuan, Ye

2016-01-01

Bone morphogenetic protein (BMP)-7 mediated neuroprotective effect of cerebral ischemic preconditioning (IPC) has been studied in an ischemic animal model, but the underlying cellular mechanisms have not been clearly clarified. In this study, primary cortical neurons and the SH-SY5Y cell line were used to investigate the role of BMP-7 and its downstream signals in the neuroprotective effects of oxygen-glucose deprivation preconditioning (OGDPC). Immunocytochemistry was used to detect the expression of neurofilament in neurons. MTT and lactate dehydrogenase activity assays were used to measure the cytotoxicity. Western blot was used to detect the protein expression of BMP-7 and downstream signals. BMP inhibitor, mitogen-activated protein kinase inhibitors, Smad inhibitor and siRNA of Smad 1 were used to investigate the role of corresponding signalling pathways in the OGDPC. Results showed that OGDPC-induced overexpression of BMP-7 in primary cortical neurons and SH-SY5Y cells. Both of endogenous and exogenous BMP-7 could replicate the neuroprotective effects seen in OGDPC pretreatment. In addition, extracellular regulated protein kinases, p38 and Smad signalling pathway were found to be involved in the neuroprotective effects mediated by OGDPC via BMP-7. This study primarily reveals the cellular mechanisms of the neuroprotection mediated by OGDPC, and provides evidence for better understanding of this intrinsic factor against ischemia. © 2015 Wiley Publishing Asia Pty Ltd.

Direct Evidence of Solution-Mediated Superoxide Transport and Organic Radical Formation in Sodium-Oxygen Batteries.

PubMed

Xia, Chun; Fernandes, Russel; Cho, Franklin H; Sudhakar, Niranjan; Buonacorsi, Brandon; Walker, Sean; Xu, Meng; Baugh, Jonathan; Nazar, Linda F

2016-09-07

Advanced large-scale electrochemical energy storage requires cost-effective battery systems with high energy densities. Aprotic sodium-oxygen (Na-O2) batteries offer advantages, being comprised of low-cost elements and possessing much lower charge overpotential and higher reversibility compared to their lithium-oxygen battery cousins. Although such differences have been explained by solution-mediated superoxide transport, the underlying nature of this mechanism is not fully understood. Water has been suggested to solubilize superoxide via formation of hydroperoxyl (HO2), but direct evidence of these HO2 radical species in cells has proven elusive. Here, we use ESR spectroscopy at 210 K to identify and quantify soluble HO2 radicals in the electrolyte-cold-trapped in situ to prolong their lifetime-in a Na-O2 cell. These investigations are coupled to parallel SEM studies that image crystalline sodium superoxide (NaO2) on the carbon cathode. The superoxide radicals were spin-trapped via reaction with 5,5-dimethyl-pyrroline N-oxide at different electrochemical stages, allowing monitoring of their production and consumption during cycling. Our results conclusively demonstrate that transport of superoxide from cathode to electrolyte leads to the nucleation and growth of NaO2, which follows classical mechanisms based on the variation of superoxide content in the electrolyte and its correlation with the crystallization of cubic NaO2. The changes in superoxide content upon charge show that charge proceeds through the reverse solution process. Furthermore, we identify the carbon-centered/oxygen-centered alkyl radicals arising from attack of these solubilized HO2 species on the diglyme solvent. This is the first direct evidence of such species, which are likely responsible for electrolyte degradation.

Atrial natriuretic peptide regulates lipid mobilization and oxygen consumption in human adipocytes by activating AMPK

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

Souza, Sandra C.; Chau, Mary D.L.; Yang, Qing

2011-07-08

Highlights: {yields} Treatment of differentiated human adipocytes with atrial natriuretic peptide (ANP) increased lipolysis and oxygen consumption by activating AMP-activated protein kinase (AMPK). {yields} ANP stimulated lipid mobilization by selective activation of the alpha2 subunit of AMPK and increased energy utilization through activation of both the alpha1 and alpha2 subunits of AMPK. {yields} ANP enhanced adipocyte mitochondrial oxidative capacity as evidenced by induction of oxidative mitochondrial genes and increase in oxygen consumption. {yields} Exposure of human adipocytes to fatty acids and (TNF{alpha}) induced insulin resistance and decreased expression of mitochondrial genes which was restored to normal by ANP. -- Abstract:more » Atrial natriuretic peptide (ANP) has been shown to regulate lipid and carbohydrate metabolism providing a possible link between cardiovascular function and metabolism by mediating the switch from carbohydrate to lipid mobilization and oxidation. ANP exerts a potent lipolytic effect via cGMP-dependent protein kinase (cGK)-I mediated-stimulation of AMP-activated protein kinase (AMPK). Activation of the ANP/cGK signaling cascade also promotes muscle mitochondrial biogenesis and fat oxidation. Here we demonstrate that ANP regulates lipid metabolism and oxygen utilization in differentiated human adipocytes by activating the alpha2 subunit of AMPK. ANP treatment increased lipolysis by seven fold and oxygen consumption by two fold, both of which were attenuated by inhibition of AMPK activity. ANP-induced lipolysis was shown to be mediated by the alpha2 subunit of AMPK as introduction of dominant-negative alpha2 subunit of AMPK attenuated ANP effects on lipolysis. ANP-induced activation of AMPK enhanced mitochondrial oxidative capacity as evidenced by a two fold increase in oxygen consumption and induction of mitochondrial genes, including carnitine palmitoyltransferase 1A (CPT1a) by 1.4-fold, cytochrome C (CytC) by 1.3-fold, and

Comparison of palladium and zirconium treated graphite tubes for in-atomizer trapping of hydrogen selenide in hydride generation electrothermal atomization atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Laborda, Francisco; Medrano, Jesús; Cortés, José I.; Mir, José M.; Castillo, Juan R.

1999-02-01

Zirconium treated graphite tubes were investigated and compared with non-treated and palladium coated ones for in situ trapping of selenium hydride generated in a flow injection system. Selenium was effectively trapped on zirconium treated tubes at trapping temperatures of 300-600°C, similar to those observed for palladium, whereas trapping temperatures higher than 600°C had to be used with non-treated tubes. Zirconium treated tubes used in this work showed good stability up to 300 trapping/atomization cycles, with precision better than 5%, characteristic masses of 42 (peak height) and 133 pg (peak area) of selenium were obtained. Sensitivity of zirconium and palladium treatments were similar, but zirconium offered the advantage of a single application per tube. Detection limits were 0.11 (peak height) and 0.23 ng (peak area) for a 1 ml sample volume.

Phase Transformation Temperatures and Solute Redistribution in a Quaternary Zirconium Alloy

NASA Astrophysics Data System (ADS)

Cochrane, C.; Daymond, M. R.

2018-05-01

This study investigates the phase stability and redistribution of solute during heating and cooling of a quaternary zirconium alloy, Excel (Zr-3.2Sn-0.8Mo-0.8Nb). Time-of-flight neutron diffraction data are analyzed using a novel Vegard's law-based approach to determine the phase fractions and location of substitutional solute atoms in situ during heating from room temperature up to 1050 °C. It is seen that this alloy exhibits direct nucleation of the β Zr phase from martensite during tempering, and stable retention of the β Zr phase to high temperatures, unlike other two-phase zirconium alloys. The transformation strains resulting from the α \\leftrightarrow β transformation are shown to have a direct impact on the development of microstructure and crystallographic texture.

Reactive Oxygen Species in Inflammation and Tissue Injury

PubMed Central

Mittal, Manish; Siddiqui, Mohammad Rizwan; Tran, Khiem; Reddy, Sekhar P.

2014-01-01

Abstract Reactive oxygen species (ROS) are key signaling molecules that play an important role in the progression of inflammatory disorders. An enhanced ROS generation by polymorphonuclear neutrophils (PMNs) at the site of inflammation causes endothelial dysfunction and tissue injury. The vascular endothelium plays an important role in passage of macromolecules and inflammatory cells from the blood to tissue. Under the inflammatory conditions, oxidative stress produced by PMNs leads to the opening of inter-endothelial junctions and promotes the migration of inflammatory cells across the endothelial barrier. The migrated inflammatory cells not only help in the clearance of pathogens and foreign particles but also lead to tissue injury. The current review compiles the past and current research in the area of inflammation with particular emphasis on oxidative stress-mediated signaling mechanisms that are involved in inflammation and tissue injury. Antioxid. Redox Signal. 20, 1126–1167. PMID:23991888

Zirconium as a Structural Material for Naval Systems

DTIC Science & Technology

1985-03-29

case with the technologically critical chemical elements chromium and cobalt, for example, from a military perspective. The case, therefore, for...By adding small amounts of tin, iron, nickel, and chromium , the impurities were effectively bound or coalesced within the metal and the corrosion...and nitrogen from the atmosphere, embrittling the weld. The techniques used for zirconium welding are gas tungsten arc welding ( GTAW ), tungsten inert

Reactive Oxygen Species Function to Mediate the Fe Deficiency Response in an Fe-Efficient Apple Genotype: An Early Response Mechanism for Enhancing Reactive Oxygen Production

PubMed Central

Sun, Chaohua; Wu, Ting; Zhai, Longmei; Li, Duyue; Zhang, Xinzhong; Xu, Xuefeng; Ma, Huiqin; Wang, Yi; Han, Zhenhai

2016-01-01

Reactive oxygen species (ROS) are important signaling molecules in plants that contribute to stress acclimation. This study demonstrated that ROS play a critical role in Fe deficiency-induced signaling at an early stage in Malus xiaojinensis. Once ROS production has been initiated, prolonged Fe starvation leads to activation of ROS scavenging mechanisms. Further, we demonstrated that ROS scavengers are involved in maintaining the cellular redox homeostasis during prolonged Fe deficiency treatment. Taken together, our results describe a feedback repression loop for ROS to preserve redox homeostasis and maintain a continuous Fe deficiency response in the Fe-efficient woody plant M. xiaojinensis. More broadly, this study reveals a new mechanism in which ROS mediate both positive and negative regulation of plant responses to Fe deficiency stress. PMID:27899933

Reactive Oxygen Species Function to Mediate the Fe Deficiency Response in an Fe-Efficient Apple Genotype: An Early Response Mechanism for Enhancing Reactive Oxygen Production.

PubMed

Sun, Chaohua; Wu, Ting; Zhai, Longmei; Li, Duyue; Zhang, Xinzhong; Xu, Xuefeng; Ma, Huiqin; Wang, Yi; Han, Zhenhai

2016-01-01

Reactive oxygen species (ROS) are important signaling molecules in plants that contribute to stress acclimation. This study demonstrated that ROS play a critical role in Fe deficiency-induced signaling at an early stage in Malus xiaojinensis . Once ROS production has been initiated, prolonged Fe starvation leads to activation of ROS scavenging mechanisms. Further, we demonstrated that ROS scavengers are involved in maintaining the cellular redox homeostasis during prolonged Fe deficiency treatment. Taken together, our results describe a feedback repression loop for ROS to preserve redox homeostasis and maintain a continuous Fe deficiency response in the Fe-efficient woody plant M. xiaojinensis . More broadly, this study reveals a new mechanism in which ROS mediate both positive and negative regulation of plant responses to Fe deficiency stress.

Singlet oxygen explicit dosimetry to predict local tumor control for HPPH-mediated photodynamic therapy

NASA Astrophysics Data System (ADS)

Penjweini, Rozhin; Kim, Michele M.; Ong, Yi Hong; Zhu, Timothy C.

2017-02-01

This preclinical study examines four dosimetric quantities (light fluence, photosensitizer photobleaching ratio, PDT dose, and reacted singlet oxygen ([1O2]rx)) to predict local control rate (LCR) for 2-(1-Hexyloxyethyl)-2-devinyl pyropheophorbide (HPPH)-mediated photodynamic therapy (PDT). Mice bearing radiation-induced fibrosarcoma (RIF) tumors were treated with different in-air fluences (135, 250 and 350 J/cm2) and in-air fluence rates (50, 75 and 150 mW/cm2) at 0.25 mg/kg HPPH and a drug-light interval of 24 hours using a 1 cm diameter collimated laser beam at 665 nm wavelength. A macroscopic model was used to calculate ([1O2]rx)) based on in vivo explicit dosimetry of the initial tissue oxygenation, photosensitizer concentration, and tissue optical properties. PDT dose was defined as a temporal integral of drug concentration and fluence rate (φ) at a 3 mm tumor depth. Light fluence rate was calculated throughout the treatment volume based on Monte-Carlo simulation and measured tissue optical properties. The tumor volume of each mouse was tracked for 30 days after PDT and Kaplan-Meier analyses for LCR were performed based on a tumor volume <=100 mm3, for four dose metrics: fluence, HPPH photobleaching rate, PDT dose, and ([1O2]rx)). The results of this study showed that ([1O2]rx)) is the best dosimetric quantity that can predict tumor response and correlate with LCR.

Do oxidized zirconium femoral heads reduce polyethylene wear in cemented THAs? A blinded randomized clinical trial.

PubMed

Zaoui, Amine; Hage, Samer El; Langlois, Jean; Scemama, Caroline; Courpied, Jean Pierre; Hamadouche, Moussa

2015-12-01

Charnley low-friction torque total hip arthroplasty (THA) remains the gold standard in THA. The main cause for failure is wear of the socket. Highly crosslinked polyethylene (HXLPE) has been associated with reduced wear rates. Also, oxidized zirconium has shown in vitro reduced wear rates. However, to our knowledge, there are no data comparing oxidized zirconium femoral heads with metal heads against HXLPE or ultrahigh-molecular-weight polyethylene (UHMWPE) when 22.25-mm bearings were used, which was the same size that performed so well in Charnley-type THAs. We hypothesized that after a minimal 4-year followup (1) use of HXLPE would result in lower radiographic wear than UHMWPE when articulating with a stainless steel head or with an oxidized zirconium head; (2) use of oxidized zirconium would result in lower radiographic wear than stainless steel when articulating with UHMWPE and HXLPE; and (3) there would be no difference in terms of Merle d'Aubigné scores between the bearing couple combinations. One hundred patients were randomized to receive cemented THA with either oxidized zirconium or a stainless steel femoral head. UHMWPE was used in the first 50 patients, whereas HXLPE was used in the next 50 patients. There were 25 patients in each of the four bearing couple combinations. All other parameters were identical in both groups. Complete followup was available in 86 of these patients. Femoral head penetration was measured using a validated computer-assisted method dedicated to all-polyethylene sockets. Clinical results were compared between the groups using the Merle d'Aubigné score. In the UHMWPE series, the median steady-state penetration rate from 1 year onward was 0.03 mm/year (range, 0.003-0.25 mm/year) in the oxidized zirconium group versus 0.11 mm/year (range, 0.03-0.29 mm/year) in the metal group (difference of medians 0.08, p < 0.001). In the HXLPE series, the median steady-state penetration rate from 1 year onward was 0.02 mm/year (range, -0.32 to

Histomorphometric and histologic evaluation of titanium-zirconium (aTiZr) implants with anodized surfaces.

PubMed

Sharma, Ajay; McQuillan, A James; Shibata, Yo; Sharma, Lavanya A; Waddell, John Neil; Duncan, Warwick John

2016-05-01

The choice of implant surface has a significant influence on osseointegration. Modification of TiZr surface by anodization is reported to have the potential to modulate the osteoblast cell behaviour favouring more rapid bone formation. The aim of this study is to investigate the effect of anodizing the surface of TiZr discs with respect to osseointegration after four weeks implantation in sheep femurs. Titanium (Ti) and TiZr discs were anodized in an electrolyte containing DL-α-glycerophosphate and calcium acetate at 300 V. The surface characteristics were analyzed by scanning electron microscopy, electron dispersive spectroscopy, atomic force microscopy and goniometry. Forty implant discs with thickness of 1.5 and 10 mm diameter (10 of each-titanium, titanium-zirconium, anodized titanium and anodized titanium-zirconium) were placed in the femoral condyles of 10 sheep. Histomorphometric and histologic analysis were performed 4 weeks after implantation. The anodized implants displayed hydrophilic, porous, nano-to-micrometer scale roughened surfaces. Energy dispersive spectroscopy analysis revealed calcium and phosphorous incorporation into the surface of both titanium and titanium-zirconium after anodization. Histologically there was new bone apposition on all implanted discs, slightly more pronounced on anodised discs. The percentage bone-to-implant contact measurements of anodized implants were higher than machined/unmodified implants but there was no significant difference between the two groups with anodized surfaces (P > 0.05, n = 10). The present histomorphometric and histological findings confirm that surface modification of titanium-zirconium by anodization is similar to anodised titanium enhances early osseointegration compared to machined implant surfaces.

Recycle of Zirconium from Used Nuclear Fuel Cladding: A Major Element of Waste Reduction

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

Collins, Emory D; DelCul, Guillermo D; Terekhov, Dmitri

2011-01-01

Feasibility tests were initiated to determine if the zirconium in commercial used nuclear fuel (UNF) cladding can be recovered in sufficient purity to permit re-use, and if the recovery process can be operated economically. Initial tests are being performed with unirradiated, non-radioactive samples of various types of Zircaloy materials that are used in UNF cladding to develop the recovery process and determine the degree of purification that can be obtained. Early results indicate that quantitative recovery can be accomplished and product contamination with alloy constituents can be controlled sufficiently to meet purification requirements. Future tests with actual radioactive UNF claddingmore » are planned. The objective of current research is to determine the feasibility of recovery and recycle of zirconium from used fuel cladding wastes. Zircaloy cladding, which contains 98+% of hafnium-free zirconium, is the second largest mass, on average {approx}25 wt %, of the components in used U.S. light-water-reactor fuel assemblies. Therefore, recovery and recycle of the zirconium would enable a large reduction in geologic waste disposal for advanced fuel cycles. Current practice is to compact or grout the cladding waste and store it for subsequent disposal in a geologic repository. This paper describes results of initial tests being performed with unirradiated, non-radioactive samples of various types of Zircaloy materials that are used in UNF cladding to develop the recovery process and determine the degree of purification that can be obtained. Future tests with actual radioactive UNF cladding are planned.« less

Electrotransport and diffusivity of molybdenum, rhenium, tungsten, and zirconium in beta-thorium

NASA Technical Reports Server (NTRS)

Schmidt, F. A.; Beck, M. S.; Rehbein, D. K.; Conzemius, R. J.; Carlson, O. N.

1984-01-01

The electric mobilities, diffusivities, and effective valences were determined for molybdenum, rhenium, tungsten, and zirconium in beta-thorium. All four solutes migrated in the same direction as the electron flow. Rhenium and molybdenum were found to be very mobile, with tungsten somewhat slower. Zirconium was found to move at a rate near that of the self-diffusion of beta-thorium, viz., about 10 to the -11th sq m/s at 1500 C. The electromigration velocities showed a similar trend. A comparison was made between experimental data obtained by scanning laser mass spectrometry and theoretical transport equations for two purification experiments. Good agreement was obtained with both the concentration profile predicted by DeGroot and the purification ratio predicted by Verhoeven.

Self-repairing vanadium-zirconium composite conversion coating for aluminum alloys

NASA Astrophysics Data System (ADS)

Zhong, Xin; Wu, Xiaosong; Jia, Yuyu; Liu, Yali

2013-09-01

In this paper, new self-repairing vanadium-zirconium composite conversion coating was prepared and investigated by Electrochemical impedance spectra (EIS), Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. EIS results showed that V-Zr conversion coating with hydrogen peroxide modified (VZO) revealed an increasing corrosion resistance in corrosive media which meant a certain self-repairing effect. SEM comparison photos also disclosed that VZO treated with scratches was gradually ameliorated from the initial cracked configuration to fewer cracks and more fillers through an immersion of 3.5% NaCl solution. XPS results demonstrated that the content of vanadium on VZO increased and zirconium declined when immersed in the corrosive solution. This explained further that the self-repairing ability could be related to vanadium. From the above results, we inferred possible structures of VZO and proposed that self-repairing effect was achieved through a hydrolysis condensation polymerization process of vanadate in the localized corrosion area.

Modification of Different Zirconium Propoxide Precursors by Diethanolamine. Is There a Shelf Stability Issue for Sol-Gel Applications?

PubMed Central

Spijksma, Gerald I.; Blank, Dave H. A.; Bouwmeester, Henny J. M.; Kessler, Vadim G.

2009-01-01

Modification of different zirconium propoxide precursors with H2dea was investigated by characterization of the isolated modified species. Upon modification of zirconium n-propoxide and [Zr(OnPr)(OiPr)3(iPrOH)]2 with ½ a mol equivalent of H2dea the complexes [Zr2(OnPr)6(OCH2CH2)2NH]2 (1) and [Zr2(OnPr)2(OiPr)4(OCH2CH2)2NH]2 (2) were obtained. However, 1H-NMR studies of these tetranuclear compounds showed that these are not time-stable either in solution or solid form. The effect of this time instability on material properties is demonstrated by light scattering and TEM experiments. Modification of zirconium isopropoxide with either ½ or 1 equivalent mol of H2dea results in formation of the trinuclear complex, Zr{η3μ2-NH(C2H4O)2}3[Zr(OiPr)3]2(iPrOH)2 (3) countering a unique nona-coordinated central zirconium atom. This complex 3 is one of the first modified zirconium propoxide precursors shown to be stable in solution for long periods of time. The particle size and morphology of the products of sol-gel synthesis are strongly dependent on the time factor and eventual heat treatment of the precursor solution. Reproducible sol-gel synthesis requires the use of solution stable precursors. PMID:20087472

Bonding of sapphire to sapphire by eutectic mixture of aluminum oxide and zirconium oxide

NASA Technical Reports Server (NTRS)

Deluca, J. J. (Inventor)

1975-01-01

Bonding of an element comprising sapphire, ruby or blue sapphire to another element of such material with a eutectic mixture of aluminum oxide and zirconium oxide is discussed. The bonding mixture may be applied in the form of a distilled water slurry or by electron beam vapor deposition. In one embodiment the eutectic is formed in situ by applying a layer of zirconium oxide and then heating the assembly to a temperature above the eutectic temperature and below the melting point of the material from which the elements are formed. The formation of a sapphire rubidium maser cell utilizing eutectic bonding is shown.

Optical properties of zirconium oxynitride films: The effect of composition, electronic and crystalline structures

NASA Astrophysics Data System (ADS)

Carvalho, P.; Borges, J.; Rodrigues, M. S.; Barradas, N. P.; Alves, E.; Espinós, J. P.; González-Elipe, A. R.; Cunha, L.; Marques, L.; Vasilevskiy, M. I.; Vaz, F.

2015-12-01

This work is devoted to the investigation of zirconium oxynitride (ZrOxNy) films with varied optical responses prompted by the variations in their compositional and structural properties. The films were prepared by dc reactive magnetron sputtering of Zr, using Ar and a reactive gas mixture of N2 + O2 (17:3). The colour of the films changed from metallic-like, very bright yellow-pale and golden yellow, for low gas flows to red-brownish for intermediate gas flows. Associated to this colour change there was a significant decrease of brightness. With further increase of the reactive gas flow, the colour of the samples changed from red-brownish to dark blue or even to interference colourations. The variations in composition disclosed the existence of four different zones, which were found to be closely related with the variations in the crystalline structure. XRD analysis revealed the change from a B1 NaCl face-centred cubic zirconium nitride-type phase for films prepared with low reactive gas flows, towards a poorly crystallized over-stoichiometric nitride phase, which may be similar to that of Zr3N4 with some probable oxygen inclusions within nitrogen positions, for films prepared with intermediate reactive gas flows. For high reactive gas flows, the films developed an oxynitride-type phase, similar to that of γ-Zr2ON2 with some oxygen atoms occupying some of the nitrogen positions, evolving to a ZrO2 monoclinic type structure within the zone where films were prepared with relatively high reactive gas flows. The analysis carried out by reflected electron energy loss spectroscopy (REELS) revealed a continuous depopulation of the d-band and an opening of an energy gap between the valence band (2p) and the Fermi level close to 5 eV. The ZrN-based coatings (zone I and II) presented intrinsic colourations, with a decrease in brightness and a colour change from bright yellow to golden yellow, red brownish and dark blue. Associated to these changes, there was also a shift

Structural studies of degradation process of zirconium dioxide tetragonal phase induced by grinding with dental bur

NASA Astrophysics Data System (ADS)

Piosik, A.; Żurowski, K.; Pietralik, Z.; Hędzelek, W.; Kozak, M.

2017-11-01

Zirconium dioxide has been widely used in dental prosthetics. However, the improper mechanical treatment can induce changes in the microstructure of zirconium dioxide. From the viewpoint of mechanical properties and performance, the phase transitions of ZrO2 from the tetragonal to the monoclinic phase induced by mechanical processing, are particularly undesirable. In this study, the phase transitions of yttrium stabilized zirconium dioxide (Y-TZP) induced by mechanical treatment are investigated by the scanning electron microscopy (SEM), atomic force microscopy (AFM) and powder diffraction (XRD). Mechanical stress was induced by different types of drills used presently in dentistry. At the same time the surface temperature was monitored during milling using a thermal imaging camera. Diffraction analysis allowed determination of the effect of temperature and mechanical processing on the scale of induced changes. The observed phase transition to the monoclinic phase was correlated with the methods of mechanical processing.

Mid-term survivorship and clinical outcomes of cobalt-chrome and oxidized zirconium on highly crosslinked polyethylene.

PubMed

Petis, Stephen M; Vasarhelyi, Edward M; Lanting, Brent A; Howard, James L; Naudie, Douglas D R; Somerville, Lyndsay E; McCalden, Richard W

2016-02-01

The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan-Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0-10.6) years for cobalt-chrome and 7.8 (range 2.1-10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%-97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%-99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%-98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%-99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up.

Mid-term survivorship and clinical outcomes of cobalt-chrome and oxidized zirconium on highly crosslinked polyethylene

PubMed Central

Petis, Stephen M.; Vasarhelyi, Edward M.; Lanting, Brent A.; Howard, James L.; Naudie, Douglas D.R.; Somerville, Lyndsay E.; McCalden, Richard W.

2016-01-01

Background The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. Methods We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan–Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. Results A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0–10.6) years for cobalt-chrome and 7.8 (range 2.1–10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%–97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%–99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%–98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%–99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Conclusion Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up. PMID:26812409

Redox polymer mediation for enzymatic biofuel cells

NASA Astrophysics Data System (ADS)

Gallaway, Joshua

Mediated biocatalytic cathodes prepared from the oxygen-reducing enzyme laccase and redox-conducting osmium hydrogels were characterized for use as cathodes in enzymatic biofuel cells. A series of osmium-based redox polymers was synthesized with redox potentials spanning the range from 0.11 V to 0.85 V (SHE), and the resulting biocatalytic electrodes were modeled to determine reaction kinetic constants using the current response, measured osmium concentration, and measured apparent electron diffusion. As in solution-phase systems, the bimolecular rate constant for mediation was found to vary greatly with mediator potential---from 250 s-1M-1 when mediator and enzyme were close in potential to 9.4 x 10 4 s-1M-1 when this overpotential was large. Optimum mediator potential for a cell operating with a non-limiting platinum anode and having no mass transport limitation from bulk solution was found to be 0.66 V (SHE). Redox polymers were synthesized under different concentrations, producing osmium variation. An increase from 6.6% to 7.2% osmium increased current response from 1.2 to 2.1 mA/cm2 for a planar film in 40°C oxygen-saturated pH 4 buffer, rotating at 900 rpm. These results translated to high surface area electrodes, nearly doubling current density to 13 mA/cm2, the highest to date for such an electrode. The typical fungal laccase from Trametes versicolor was replaced by a bacterially-expressed small laccase from Streptomyces coelicolor, resulting in biocatalytic films that reduced oxygen at increased pH, with full functionality at pH 7, producing 1.5 mA/cm 2 in planar configuration. Current response was biphasic with pH, matching the activity profile of the free enzyme in solution. The mediated enzyme electrode system was modeled with respect to apparent electron diffusion, mediator concentration, and transport of oxygen from bulk solution, all of which are to some extent controlled by design. Each factor was found to limit performance in certain circumstances

Total knee arthroplasty with an oxidised zirconium femoral component: ten-year survivorship analysis.

PubMed

Ahmed, I; Salmon, L J; Waller, A; Watanabe, H; Roe, J P; Pinczewski, L A

2016-01-01

Oxidised zirconium was introduced as a material for femoral components in total knee arthroplasty (TKA) as an attempt to reduce polyethylene wear. However, the long-term survival of this component is not known. We performed a retrospective review of a prospectively collected database to assess the ten year survival and clinical and radiological outcomes of an oxidised zirconium total knee arthroplasty with the Genesis II prosthesis. The Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC), Knee Injury and Osteoarthritis Outcome Score (KOOS) and a patient satisfaction scale were used to assess outcome. A total of 303 consecutive TKAs were performed in 278 patients with a mean age of 68 years (45 to 89). The rate of survival ten years post-operatively as assessed using Kaplan-Meier analysis was 97% (95% confidence interval 94 to 99) with revision for any reason as the endpoint. There were no revisions for loosening, osteolysis or failure of the implant. There was a significant improvement in all components of the WOMAC score at final follow-up (p < 0.001). The mean individual components of the KOOS score for symptoms (82.4 points; 36 to 100), pain (87.5 points; 6 to 100), activities of daily life (84.9 points; 15 to 100) and quality of life (71.4 points; 6 to 100) were all at higher end of the scale. This study provides further supportive evidence that the oxidised zirconium TKA gives comparable rates of survival with other implants and excellent functional outcomes ten years post-operatively. Total knee arthroplasty with an oxidised zirconium femoral component gives comparable long-term rates of survival and functional outcomes with conventional implants. ©2016 The British Editorial Society of Bone & Joint Surgery.

SirT1 mediates hyperbaric oxygen preconditioning-induced ischemic tolerance in rat brain

PubMed Central

Yan, Wenjun; Fang, Zongping; Yang, Qianzi; Dong, Hailong; Lu, Yan; Lei, Chong; Xiong, Lize

2013-01-01

Our previous studies have shown that hyperbaric oxygen preconditioning (HBO-PC) induces tolerance to cerebral ischemia/reperfusion (I/R). This study aimed to investigate whether SirT1, a class III histone deacetylase, is involved in neuroprotection elicited by HBO-PC in animal and cell culture models of ischemia. Rats were subjected to middle cerebral artery occlusion for 120 minutes after HBO-PC (once a day for 5 days). Primary cultured cortical neurons were exposed to 2 hours of HBO-PC after 2 hours of oxygen–glucose deprivation (OGD). We showed that HBO-PC increased SirT1 protein and mRNA expression, promoted neurobehavioral score, reduced infarct volume, and improved morphology at 24 hours and 7 days after cerebral I/R. Neuroprotection of HBO-PC was attenuated by SirT1 inhibitor EX527 and SirT1 knockdown by short interfering RNA (siRNA), whereas it was mimicked by SirT1 activator resveratrol. Furthermore, HBO-PC enhanced SirT1 expression and cell viability and reduced lactate dehydrogenase release 24 hours after OGD/re-oxygenation. The neuroprotective effect of HBO-PC was emulated through upregulating SirT1 and, reversely, attenuated through downregulating SirT1. The modulation of SirT1 was made by adenovirus infection carrying SirT1 or SirT1 siRNA. Besides, SirT1 increased B-cell lymphoma 2 (Bcl-2) expression and decrease cleaved caspase 3. These results indicate that SirT1 mediates HBO-PC-induced tolerance to cerebral I/R through inhibition of apoptosis. PMID:23299244

High performance polymer solar cells with as-prepared zirconium acetylacetonate film as cathode buffer layer

PubMed Central

Tan, Zhan'ao; Li, Shusheng; Wang, Fuzhi; Qian, Deping; Lin, Jun; Hou, Jianhui; Li, Yongfang

2014-01-01

Low-work-function active metals are commonly used as cathode in polymer solar cells (PSCs), but sensitivity of the active metals towards moisture and oxygen results in poor stability of the devices. Therefore, solution-proceessable and stable cathode buffer layer is of great importance for the application of PSCs. Here we demonstrate high performance PSCs by employing as-prepared zirconium acetylacetonate (a-ZrAcac) film spin-cast from its ethanol solution as cathode buffer layer. The PSCs based on a low bandgap polymer PBDTBDD as donor and PC60BM as acceptor with a-ZrAcac/Al cathode demonstrated an average power conversion efficiency (PCE) of 8.75% which is significantly improved than that of the devices with traditional Ca/Al cathode. The improved photovoltaic performance is benefitted from the decreased series resistance and enhanced light harvest of the PSCs with the a-ZrAcac/Al cathode. The results indicate that a-ZrAcac is a promising high performance cathode buffer layer for fabricating large area flexible PSCs. PMID:24732976

[How did the earth's oxygen atmosphere originate?].

PubMed

Schäfer, G

2004-09-01

The planet earth did not carry an oxygen atmosphere from the beginning. Though oxygen could arise from radiation mediated water splitting, these processes were not efficient enough to create a global gas atmosphere. Oxygen in the latter is a product of the photosynthetic activity of early green organisms. Only after biological mass-formation of oxygen the UV-protective ozone layer could develop, then enabeling life to move from water onto land. This took billions of years. The basics of the processes of biological oxygen liberation and utilization are described in the following as well as the importance of their steady state equilibrium. Also a hint is given to oxygen as a toxic compound though being a chemical prerequisite for aerobic life on earth.

Oxygen Consumption and Usage During Physical Exercise: The Balance Between Oxidative Stress and ROS-Dependent Adaptive Signaling

PubMed Central

Zhao, Zhongfu; Koltai, Erika; Ohno, Hideki; Atalay, Mustafa

2013-01-01

Abstract The complexity of human DNA has been affected by aerobic metabolism, including endurance exercise and oxygen toxicity. Aerobic endurance exercise could play an important role in the evolution of Homo sapiens, and oxygen was not important just for survival, but it was crucial to redox-mediated adaptation. The metabolic challenge during physical exercise results in an elevated generation of reactive oxygen species (ROS) that are important modulators of muscle contraction, antioxidant protection, and oxidative damage repair, which at moderate levels generate physiological responses. Several factors of mitochondrial biogenesis, such as peroxisome proliferator-activated receptor-γ coactivator 1α (PGC-1α), mitogen-activated protein kinase, and SIRT1, are modulated by exercise-associated changes in the redox milieu. PGC-1α activation could result in decreased oxidative challenge, either by upregulation of antioxidant enzymes and/or by an increased number of mitochondria that allows lower levels of respiratory activity for the same degree of ATP generation. Endogenous thiol antioxidants glutathione and thioredoxin are modulated with high oxygen consumption and ROS generation during physical exercise, controlling cellular function through redox-sensitive signaling and protein–protein interactions. Endurance exercise-related angiogenesis, up to a significant degree, is regulated by ROS-mediated activation of hypoxia-inducible factor 1α. Moreover, the exercise-associated ROS production could be important to DNA methylation and post-translation modifications of histone residues, which create heritable adaptive conditions based on epigenetic features of chromosomes. Accumulating data indicate that exercise with moderate intensity has systemic and complex health-promoting effects, which undoubtedly involve regulation of redox homeostasis and signaling. Antioxid. Redox Signal. 18, 1208–1246. PMID:22978553

Manufacturing process to reduce large grain growth in zirconium alloys

DOEpatents

Rosecrans, Peter M.

1987-01-01

A method of treating cold-worked zirconium alloys to reduce large grain gth during thermal treatment at temperatures above the recrystallization temperature of the alloy comprising heating the cold-worked alloy between about 1300.degree.-1350.degree. F. for 1 to 3 hours prior to treatment above its recrystallization temperature.

Assessment of wear coefficients of nuclear zirconium claddings without and with pre-oxidation

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

Qu, Jun; Cooley, Kevin M.; Shaw, Austin H.

In the cores of pressurized water nuclear reactors, water-flow induced vibration is known to cause claddings on the fuel rods to rub against their supporting grids. Such grid-to-rod-fretting (GTRF) may lead to fretting wear-through and the leakage of radioactive species. The surfaces of actual zirconium alloy claddings in a reactor are inevitably oxidized in the high-temperature pressurized water, and some claddings are even pre-oxidized. As a result, the wear process of the surface oxide film is expected to be quite different from the zirconium alloy substrate. In this paper, we attempt to measure the wear coefficients of zirconium claddings withoutmore » and with pre-oxidation rubbing against grid samples using a bench-scale fretting tribometer. Results suggest that the volumetric wear coefficient of the pre-oxidized cladding is 50 to 200 times lower than that of the untreated cladding. In terms of the linear rate of wear depth, the pre-oxidized alloy wears about 15 times more slowly than the untreated cladding. Finally, fitted with the experimentally-determined wear rates, a stage-wise GTRF engineering wear model demonstrates good agreement with in-reactor experience in predicting the trend of cladding lives.« less

Assessment of wear coefficients of nuclear zirconium claddings without and with pre-oxidation

DOE PAGES

Qu, Jun; Cooley, Kevin M.; Shaw, Austin H.; ...

2016-03-16

In the cores of pressurized water nuclear reactors, water-flow induced vibration is known to cause claddings on the fuel rods to rub against their supporting grids. Such grid-to-rod-fretting (GTRF) may lead to fretting wear-through and the leakage of radioactive species. The surfaces of actual zirconium alloy claddings in a reactor are inevitably oxidized in the high-temperature pressurized water, and some claddings are even pre-oxidized. As a result, the wear process of the surface oxide film is expected to be quite different from the zirconium alloy substrate. In this paper, we attempt to measure the wear coefficients of zirconium claddings withoutmore » and with pre-oxidation rubbing against grid samples using a bench-scale fretting tribometer. Results suggest that the volumetric wear coefficient of the pre-oxidized cladding is 50 to 200 times lower than that of the untreated cladding. In terms of the linear rate of wear depth, the pre-oxidized alloy wears about 15 times more slowly than the untreated cladding. Finally, fitted with the experimentally-determined wear rates, a stage-wise GTRF engineering wear model demonstrates good agreement with in-reactor experience in predicting the trend of cladding lives.« less

Modification and intercalation of layered zirconium phosphates: a solid-state NMR monitoring.

PubMed

Bakhmutov, Vladimir I; Kan, Yuwei; Sheikh, Javeed Ahmad; González-Villegas, Julissa; Colón, Jorge L; Clearfield, Abraham

2017-07-01

Several layered zirconium phosphates treated with Zr(IV) ions, modified by monomethoxy-polyethyleneglycol-monophosphate and intercalated with doxorubicin hydrochloride have been studied by solid-state MAS NMR techniques. The organic components of the phosphates have been characterized by the 13 C{ 1 H} CP MAS NMR spectra compared with those of initial compounds. The multinuclear NMR monitoring has provided to establish structure and covalent attachment of organic/inorganic moieties to the surface and interlayer spaces of the phosphates. The MAS NMR experiments including kinetics of proton-phosphorus cross polarization have resulted in an unusual structure of zirconium phosphate 6 combining decoration of the phosphate surface by polymer units and their partial intercalation into the interlayer space. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Electrochemical Study of Corrosion Phenomena in Zirconium Alloys

DTIC Science & Technology

2005-06-01

required reaction rates [1.1]. Based predominantly on this fact, zirconium alloys were chosen to sheath, or clad, the fuel. With the increasing demand...cathode or anode. As the oxidation and reduction reactions occur, a galvanic cell is developed. The electrons on the anode are released from the metallic...matrix as the ions are released into the aqueous solution in the initial half-cell reaction . The second half-cell reaction , taking place on the

RNA sequencing supports distinct reactive oxygen species-mediated pathways of apoptosis by high and low size mass fractions of Bay leaf (Lauris nobilis) in HT-29 cells.

PubMed

Rodd, Annabelle L; Ververis, Katherine; Sayakkarage, Dheeshana; Khan, Abdul W; Rafehi, Haloom; Ziemann, Mark; Loveridge, Shanon J; Lazarus, Ross; Kerr, Caroline; Lockett, Trevor; El-Osta, Assam; Karagiannis, Tom C; Bennett, Louise E

2015-08-01

Anti-proliferative and pro-apoptotic effects of Bay leaf (Laurus nobilis) in mammalian cancer and HT-29 adenocarcinoma cells have been previously attributed to effects of polyphenolic and essential oil chemical species. Recently, we demonstrated differentiated growth-regulating effects of high (HFBL) versus low molecular mass (LFBL) aqueous fractions of bay leaf and now confirm by comparative effects on gene expression, that HFBL and LFBL suppress HT-29 growth by distinct mechanisms. Induction of intra-cellular lesions including DNA strand breakage by extra-cellular HFBL, invoked the hypothesis that iron-mediated reactive oxygen species with capacity to penetrate cell membrane, were responsible for HFBL-mediated effects, supported by equivalent effects of HFBL in combination with γ radiation. Activities of HFBL and LFBL were interpreted to reflect differentiated responses to iron-mediated reactive oxygen species (ROS), occurring either outside or inside cells. In the presence of LFBL, apoptotic death was relatively delayed compared with HFBL. ROS production by LFBL mediated p53-dependent apoptosis and recovery was suppressed by promoting G1/S phase arrest and failure of cellular tight junctions. In comparison, intra-cellular anti-oxidant protection exerted by LFBL was absent for extra-cellular HFBL (likely polysaccharide-rich), which potentiated more rapid apoptosis by producing DNA double strand breaks. Differentiated effects on expression of genes regulating ROS defense and chromatic condensation by LFBL versus HFBL, were observed. The results support ferrous iron in cell culture systems and potentially in vivo, can invoke different extra-cellular versus intra-cellular ROS-mediated chemistries, that may be regulated by exogenous, including dietary species.

Enhancement of yield strength in zirconium metal through high-pressure induced structural phase transition

NASA Astrophysics Data System (ADS)

Zhao, Yusheng; Zhang, Jianzhong

2007-11-01

We report here a high-pressure phase-transition induced strengthening in ultrapure zirconium metal. The determined yield strength shows more than sixfold abrupt increase at the transition pressure of Pc=6GPa, from σyα≈180MPa in the low-pressure phase of α-Zr to σyω≈1180MPa in the high-pressure phase of ω-Zr. The observed enhancement provides an alternate route for material strengthening and is the most significant among the known strengthening techniques for metals. Our findings support the theoretical simulations of the substantial covalent bonding and "rougher" corrugation of slip planes for dislocations in the ω-phase of zirconium.

Decay properties and reaction dynamics of zirconium isotopes in the relativistic mean-field model

NASA Astrophysics Data System (ADS)

Panigrahi, M.; Panda, R. N.; Kumar, Bharat; Patra, S. K.

In the framework of relativistic mean-field theory, the ground state properties like binding energy, charge radius and quadrupole deformation parameter for various isotopes of zirconium from the valley of stability to drip-line region have been studied. The results are compared with the experimental data and we found reasonable agreement. The calculations are carried out for β-decay energy and β-decay half-life up to the drip-line. Total reaction and elastic differential cross-sections are also studied for few zirconium isotopes as projectiles with 12C as target, using different parameter sets namely NL3*, DD-ME2 and DD-PC1 in conjunction with Glauber model.

Method to predict relative hydriding within a group of zirconium alloys under nuclear irradiation

DOEpatents

Johnson, A.B. Jr.; Levy, I.S.; Trimble, D.J.; Lanning, D.D.; Gerber, F.S.

1990-04-10

An out-of-reactor method for screening to predict relative in-reactor hydriding behavior of zirconium-based materials is disclosed. Samples of zirconium-based materials having different compositions and/or fabrication methods are autoclaved in a relatively concentrated (0.3 to 1.0M) aqueous lithium hydroxide solution at constant temperatures within the water reactor coolant temperature range (280 to 316 C). Samples tested by this out-of-reactor procedure, when compared on the basis of the ratio of hydrogen weight gain to oxide weight gain, accurately predict the relative rate of hydriding for the same materials when subject to in-reactor (irradiated) corrosion. 1 figure.

Method to predict relative hydriding within a group of zirconium alloys under nuclear irradiation

DOEpatents

Johnson, Jr., A. Burtron; Levy, Ira S.; Trimble, Dennis J.; Lanning, Donald D.; Gerber, Franna S.

1990-01-01

An out-of-reactor method for screening to predict relative in-reactor hydriding behavior of zirconium-bsed materials is disclosed. Samples of zirconium-based materials having different composition and/or fabrication are autoclaved in a relatively concentrated (0.3 to 1.0M) aqueous lithium hydroxide solution at constant temperatures within the water reactor coolant temperature range (280.degree. to 316.degree. C.). Samples tested by this out-of-reactor procedure, when compared on the basis of the ratio of hydrogen weight gain to oxide weight gain, accurately predict the relative rate of hyriding for the same materials when subject to in-reactor (irradiated) corrision.

Dynamic activation of Src induced by low-power laser irradiation in living cells mediated by reactive oxygen species

NASA Astrophysics Data System (ADS)

Zhang, Juntao; Gao, Xuejuan; Xing, Da; Liu, Lei

2007-11-01

Low-power laser irradiation (LPLI) leads to photochemical reaction and then activates intracellular several signaling pathway. Reactive oxygen species (ROS) are considered to be the primary messengers produced by LPLI. Here, we studied the signaling pathway mediated by ROS upon the stimulation of LPLI. Src tyrosine kinases are well-known targets of ROS and can be activated by oxidative events. Using a Src reporter based on fluorescence resonance energy transfer (FRET) technique, we visualized the dynamic Src activation in Hela cells immediately after LPLI. Moreover, Src activity was enhanced by increasing the duration of LPLI. In addition, our results suggested that ROS were key mediators of Src activation, as ROS scavenger, vitamin C decreased and exogenous H IIO II increased the activity of Src. Meanwhile, Gö6983 loading did not block the effect of LPLI. CCK-8 experiments proved that cell vitality was prominently improved by LPLI with all the doses we applied in our experiments ranging from 3 to 25J/cm2. The results indicated that LPLI/ROS/Src pathway may be involved in the LPLI biostimulation effects.

Introduction of oxygen vacancies and fluorine into TiO{sub 2} nanoparticles by co-milling with PTFE

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

Senna, Mamoru, E-mail: senna@applc.keio.ac.jp; Sepelak, Vladimir; Shi, Jianmin

2012-03-15

Solid-state processes of introducing oxygen vacancies and transference of fluorine to n-TiO{sub 2} nanoparticles by co-milling with poly(tetrafluoroethylene) (PTFE) powder were examined by diffuse reflectance spectroscopy (DRS) of UV, visual, near- and mid-IR regions, thermal analyses (TG-DTA), energy-dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The broad absorption peak at around 8800 cm{sup -1} (1140 nm) was attributed to the change in the electronic states, viz. electrons trapped at the oxygen vacancies (Vo) and d-d transitions of titanium ions. Incorporation of fluorine into n-TiO{sub 2} was concentrated at the near surfacemore » region and amounted to ca. 40 at% of the total fluorine in PTFE, after co-milling for 3 h, as confirmed by the F1s XPS spectrum. The overall atomic ratio, F/Ti, determined by EDXS was 0.294. By combining these analytical results, a mechanism of the present solid state processes at the boundary between PTFE and n-TiO{sub 2} was proposed. The entire process is triggered by the partial oxidative decomposition of PTFE. This is accompanied by the abstraction of oxygen atoms from the n-TiO{sub 2} lattices. Loss of the oxygen atoms results in the formation of the diverse states of locally distorted coordination units of titania, i.e. TiO{sub 6-n}Vo{sub n}, located at the near surface region. This leads subsequent partial ligand exchange between F and O, to incorporate fluorine preferentially to the near surface region of n-TiO{sub 2} particles, where local non-crystalline states predominate. - Graphical abstract: Scheme of the reaction processes: (a) pristine mixture, (b) oxygen abstraction from TiO{sub 2} and (c) fluorine migration from PTFE to TiO{sub 2}. Highlights: Transfer of fluorine from PTFE to n-TiO{sub 2} in a dry solid state process was confirmed. Black-Right-Pointing-Pointer 40% of F in PTFE was incorporated to

Bioconjugation of zirconium uridine monophosphate: application to myoglobin direct electrochemistry.

PubMed

Qiao, Yuanbiao; Jian, Fangfang; Bai, Qian

2008-03-14

Porous nano-granule of zirconium uridine monophosphate, Zr(UMP)2.H2O is, for the first time, synthesized under mild experimental conditions and applied to the bioconjugation of myoglobin (Mb) to realize its direct electron transfer. UV-vis and resonance Raman spectroscopies prove that Mb in the Zr(UMP)2.H2O film maintains its secondary structure similar to the native state. The conjugation film of the Mb-Zr(UMP)2.H2O on the glassy carbon (GC) electrode gives a well-defined and quasi-reversible cyclic voltammogram, which reflects the direct electron transfer of the heme Fe III/Fe II couple of Mb. On the basis of the satisfying bioelectrocatalysis of the nano-conjugation of Mb and genetic substrate, a kind of mediator-free biosensor for H2O2 is developed. The linear range for H2O2 detection is estimated to be 3.92-180.14 microM. The apparent Michaelis-Menten constant (Km) and the detection limit based on the signal-to-noise ratio of 3 are found to be 196.1 microM and 1.52 microM, respectively. Both the apparent Michaelis-Menten constant and the detection limit herein are much lower than currently reported values from other Mb films. This kind of sensor possesses excellent stability, long-term life (more than 20 days) and good reproducibility.

Structural environments of incompatible elements in silicate glass/melt systems: I. Zirconium at trace levels

NASA Astrophysics Data System (ADS)

Farges, Franã§Ois; Ponader, Carl W.; Brown, Gordon E., Jr.

1991-06-01

The structural environments of trace levels (2˜000 ppm) of Zr 4+ in several silicate glasses were examined as a function of melt composition and polymerization using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Glass compositions investigated were albite (NaAlSi 3O 8: AB) and a peralkaline composition (Na 3.3AlSi 7O 17: PR)- Zirconium was added to the oxide-carbonate mix prior to melting in the form of ZrO 2 (baddeleyite). A second set of Zr-silicate glasses containing 2000 ppm Zr and 1.0 to 2.4 wt% halogens (F as NaF and Cl as NaCl) was also synthesized. These included the Zr-AB and Zr-PR base-glass compositions as well as Zr-sodium trisilicate composition (Na2Si 3O 7: TS). In all glasses studied, Zr is mainly 6-coordinated by oxygen atoms ( d[Zr-O] ˜2.07 ± 0.01 Å). In the most polymerized glass (AB), a small but significant amount of Zr was also found to occur in 8-coordinated sites ( d[Zr-O] ˜2.22 Å). No clear evidence for F or Cl complexes of Zr was observed in any of the halogen-containing glasses. The regularity of the Zr site increases in the series AB < TS ˜PR. We attribute this change to an increase in the number of non-bridging oxygens in the first-coordination sphere of Zr related to the depolymerizing effects of halogens and/or sodium. Minor but significant interactions of Zr with the tetrahedral network were observed ( d[Zr-{Si, Al}] ˜3.65-3.71 Å ± 0.03 Å), which are consistent with Zr-O-{Si, Al} angles close to 160-170°, as in catapleiite (Na 2ZrSi 3O 9 · 2H 2O). Intermediaterange order, as reflected by the presence and number of second-neighbor {Si, Al} around Zr, increases significantly with increasing melt polymerization. The local environment around Zr is more strongly influenced by bonding requirements than by the network topology of the melt. Stabilization of zirconium in 6-coordinated sites in relatively depolymerized melts should act to decrease the crystal-melt partition coefficients of Zr and may explain the

The role of hemoglobin oxygen affinity in oxygen transport at high altitude.

PubMed

Winslow, Robert M

2007-09-30

Hemoglobin is involved in the regulation of O(2) transport in two ways: a long-term adjustment in red cell mass is mediated by erythropoietin (EPO), a response to renal oxgyenation. Short-term, rapid-response adjustments are mediated by ventilation, cardiac output, hemoglobin oxygen affinity (P50), barriers to O(2) diffusion, and the control of local microvascular tissue perfusion. The distribution of O(2) between dissolved (PO2) and hemoglobin-bound (saturation) is the familiar oxygen equilibrium curve, whose position is noted as P50. Human hemoglobin is not genetically adapted for function at high altitude. However, more specialized species native to high altitudes (guinea pig and bar-headed goose, for example) seem to have a lower P50 than their sea level counterparts, an adaptation that presumably promotes O(2) uptake from a hypoxic environment. Humans, native to very high altitude either in the Andes or Himalayan mountains, also can increase O(2) affinity, not because of a fundamental difference in hemoglobin structure or function, but because of extreme hyperventilation and alkalosis.

Wear Analysis in THA Utilizing Oxidized Zirconium and Crosslinked Polyethylene

PubMed Central

Garvin, Kevin L.; Mangla, Jimmi; Murdoch, Nathan; Martell, John M.

2008-01-01

Oxidized zirconium, a material with a ceramic surface on a metal substrate, and highly cross-linked polyethylene are two materials developed to reduce wear. We measured in vivo femoral head penetration in patients with these advanced bearings. We hypothesized the linear wear rates would be lower than those published for cobalt-chrome and standard polyethylene. We retrospectively reviewed a select series of 56 THAs in a relatively young, active patient population utilizing oxidized zirconium femoral heads and highly cross-linked polyethylene acetabular liners. Femoral head penetration was determined using the Martell computerized edge-detection method. All patients were available for 2-year clinical and radiographic followup. True linear wear was 4 μm/year (95% confidence intervals, ± 59 μm/year). The early wear rates in this cohort of relatively young, active patients were low and we believe justify the continued study of these alternative bearing surfaces. Level of Evidence: Level IV, therapeutic study. See the Guidelines for Authors for a complete description of levels of evidence. PMID:18946711

Structure and Thermodynamical Properties of Zirconium Hydrides from First-Principle

NASA Astrophysics Data System (ADS)

Blomqvist, Jakob; Olofsson, Johan; Alvarez, Anna-Maria; Bjerkén, Christina

Zirconium alloys are used as nuclear fuel cladding material due to their mechanical and corrosion resistant properties together with their favorable cross-section for neutron scattering. At running conditions, however, there will be an increase of hydrogen in the vicinity of the cladding surface at the water side of the fuel. The hydrogen will diffuse into the cladding material and at certain conditions, such as lower temperatures and external load, hydrides will precipitate out in the material and cause well known embrittlement, blistering and other unwanted effects. Using phase-field methods it is now possible to model precipitation buildup in metals, for example as a function of hydrogen concentration, temperature and external load, but the technique relies on input of parameters, such as the formation energy of the hydrides and matrix. To that end, we have computed, using the density functional theory (DFT) code GPAW, the latent heat of fusion as well as solved the crystal structure for three zirconium hydride polymorphs: δ-ZrH1.6, γ-ZrH, and Є-ZrH2.

Effects of different titanium zirconium implant surfaces on initial supragingival plaque formation.

PubMed

John, Gordon; Becker, Jürgen; Schwarz, Frank

2017-07-01

The aim of the current study was the evaluation of biofilm development on different implant surfaces. Initial biofilm formation was investigated on five different implant surfaces, machined titanium (MTi), modified machined acid-etched titanium (modMATi), machined titanium zirconium (MTiZr), modified machined and acid-etched titanium zirconium (modMATiZr) and sandblasted large grid and acid-etched titanium zirconium surface (SLATiZr) for 24 and 48 h. Biocompatibility was tested after tooth brushing of the samples via cell viability testing with human gingival fibroblasts. After 24 h of biofilm collection, mean plaque surface was detected in the following descending order: After 24 h: MTiZr > MTi > SLATiZr > modMATiZr > modMATi. Both M surfaces showed significant higher biofilm formation than the other groups. After 48 h: MTiZr > MTi > SLATiZr > modMATiZr > modMATi. After tooth brushing: SLATiZr > modMATi > modMATiZr > MTi > MTiZr. All native samples depicted significant higher cell viability than their corresponding surfaces after biofilm removal procedure. The TiZr groups especially the modMATiZr group showed slower and less biofilm formation. In combination with the good biocompatibility, both modMA surfaces seem to be interesting candidates for surfaces in transgingival implant design. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Toxin detection using a tyrosinase-coupled oxygen electrode.

PubMed

Smit, M H; Rechnitz, G A

1993-02-15

An enzyme-based "electrochemical canary" is described for the detection of cyanide. The sensing system imitates cyanide's site of toxicity in the mitochondria. The terminal sequence of electron transfer in aerobic respiration is mimicked by mediator coupling of tyrosinase catalysis to an electro-chemical system. An enzyme-coupled oxygen electrode is created which is sensitive to selective poisoning. Biocatalytic reduction of oxygen is promoted by electrochemically supplying tyrosinase with electrons. Thus, ferrocyanide is generated at a cathode and mediates the enzymatic reduction of oxygen to water. An enzyme-dependent reductive current can be monitored which is inhibited by cyanide in a concentration-dependent manner. Oxygen depletion in the reaction layer can be minimized by addressing enzyme activity using a potential pulsing routine. Enzyme activity is electrochemically initiated and terminated and the sensor becomes capable of continuous monitoring. Cyanide poisoning of the biological component is reversible, and it can be reused after rinsing. The resulting sensor detects cyanide based on its biological activity rather than its physical or chemical properties.

A Comparison of Singlet Oxygen Explicit Dosimetry (SOED) and Singlet Oxygen Luminescence Dosimetry (SOLD) for Photofrin-Mediated Photodynamic Therapy

PubMed Central

Kim, Michele M.; Penjweini, Rozhin; Gemmell, Nathan R.; Veilleux, Israel; McCarthy, Aongus; Buller, Gerald S.; Hadfield, Robert H.; Wilson, Brian C.; Zhu, Timothy C.

2016-01-01

Accurate photodynamic therapy (PDT) dosimetry is critical for the use of PDT in the treatment of malignant and nonmalignant localized diseases. A singlet oxygen explicit dosimetry (SOED) model has been developed for in vivo purposes. It involves the measurement of the key components in PDT—light fluence (rate), photosensitizer concentration, and ground-state oxygen concentration ([3O2])—to calculate the amount of reacted singlet oxygen ([1O2]rx), the main cytotoxic component in type II PDT. Experiments were performed in phantoms with the photosensitizer Photofrin and in solution using phosphorescence-based singlet oxygen luminescence dosimetry (SOLD) to validate the SOED model. Oxygen concentration and photosensitizer photobleaching versus time were measured during PDT, along with direct SOLD measurements of singlet oxygen and triplet state lifetime (τΔ and τt), for various photosensitizer concentrations to determine necessary photophysical parameters. SOLD-determined cumulative [1O2]rx was compared to SOED-calculated [1O2]rx for various photosensitizer concentrations to show a clear correlation between the two methods. This illustrates that explicit dosimetry can be used when phosphorescence-based dosimetry is not feasible. Using SOED modeling, we have also shown evidence that SOLD-measured [1O2]rx using a 523 nm pulsed laser can be used to correlate to singlet oxygen generated by a 630 nm laser during a clinical malignant pleural mesothelioma (MPM) PDT protocol by using a conversion formula. PMID:27929427

A Comparison of Singlet Oxygen Explicit Dosimetry (SOED) and Singlet Oxygen Luminescence Dosimetry (SOLD) for Photofrin-Mediated Photodynamic Therapy.

PubMed

Kim, Michele M; Penjweini, Rozhin; Gemmell, Nathan R; Veilleux, Israel; McCarthy, Aongus; Buller, Gerald S; Hadfield, Robert H; Wilson, Brian C; Zhu, Timothy C

2016-12-06

Accurate photodynamic therapy (PDT) dosimetry is critical for the use of PDT in the treatment of malignant and nonmalignant localized diseases. A singlet oxygen explicit dosimetry (SOED) model has been developed for in vivo purposes. It involves the measurement of the key components in PDT-light fluence (rate), photosensitizer concentration, and ground-state oxygen concentration ([³ O ₂])-to calculate the amount of reacted singlet oxygen ([¹ O ₂] rx ), the main cytotoxic component in type II PDT. Experiments were performed in phantoms with the photosensitizer Photofrin and in solution using phosphorescence-based singlet oxygen luminescence dosimetry (SOLD) to validate the SOED model. Oxygen concentration and photosensitizer photobleaching versus time were measured during PDT, along with direct SOLD measurements of singlet oxygen and triplet state lifetime ( τ Δ and τ t ), for various photosensitizer concentrations to determine necessary photophysical parameters. SOLD-determined cumulative [¹ O ₂] rx was compared to SOED-calculated [¹ O ₂] rx for various photosensitizer concentrations to show a clear correlation between the two methods. This illustrates that explicit dosimetry can be used when phosphorescence-based dosimetry is not feasible. Using SOED modeling, we have also shown evidence that SOLD-measured [¹ O ₂] rx using a 523 nm pulsed laser can be used to correlate to singlet oxygen generated by a 630 nm laser during a clinical malignant pleural mesothelioma (MPM) PDT protocol by using a conversion formula.

Multiphysics phase field modeling of hydrogen diffusion and delta-hydride precipitation in alpha-zirconium

NASA Astrophysics Data System (ADS)

Jokisaari, Andrea M.

Hydride precipitation in zirconium is a significant factor limiting the lifetime of nuclear fuel cladding, because hydride microstructures play a key role in the degradation of fuel cladding. However, the behavior of hydrogen in zirconium has typically been modeled using mean field approaches, which do not consider microstructural evolution. This thesis describes a quantitative microstructural evolution model for the alpha-zirconium/delta-hydride system and the associated numerical methods and algorithms that were developed. The multiphysics, phase field-based model incorporates CALPHAD free energy descriptions, linear elastic solid mechanics, and classical nucleation theory. A flexible simulation software implementing the model, Hyrax, is built on the Multiphysics Object Oriented Simulation Environment (MOOSE) finite element framework. Hyrax is open-source and freely available; moreover, the numerical methods and algorithms that have been developed are generalizable to other systems. The algorithms are described in detail, and verification studies for each are discussed. In addition, analyses of the sensitivity of the simulation results to the choice of numerical parameters are presented. For example, threshold values for the CALPHAD free energy algorithm and the use of mesh and time adaptivity when employing the nucleation algorithm are studied. Furthermore, preliminary insights into the nucleation behavior of delta-hydrides are described. These include a) the sensitivities of the nucleation rate to temperature, interfacial energy, composition and elastic energy, b) the spatial variation of the nucleation rate around a single precipitate, and c) the effect of interfacial energy and nucleation rate on the precipitate microstructure. Finally, several avenues for future work are discussed. Topics encompass the terminal solid solubility hysteresis of hydrogen in zirconium and the effects of the alpha/delta interfacial energy, as well as thermodiffusion, plasticity

Method for calcining nuclear waste solutions containing zirconium and halides

DOEpatents

Newby, Billie J.

1979-01-01

A reduction in the quantity of gelatinous solids which are formed in aqueous zirconium-fluoride nuclear reprocessing waste solutions by calcium nitrate added to suppress halide volatility during calcination of the solution while further suppressing chloride volatility is achieved by increasing the aluminum to fluoride mole ratio in the waste solution prior to adding the calcium nitrate.

Experimental Calcium Silicate-Based Cement with and without Zirconium Oxide Modulates Fibroblasts Viability.

PubMed

Slompo, Camila; Peres-Buzalaf, Camila; Gasque, Kellen Cristina da Silva; Damante, Carla Andreotti; Ordinola-Zapata, Ronald; Duarte, Marco Antonio Hungaro; de Oliveira, Rodrigo Cardoso

2015-01-01

The aim of this study was to verify whether the use of zirconium oxide as a radiopacifier of an experimental calcium silicate-based cement (WPCZO) leads to cytotoxicity. Fibroblasts were treated with different concentrations (10 mg/mL, 1 mg/mL, and 0.1 mg/mL) of the cements diluted in Dulbecco's modified Eagle's medium (DMEM) for periods of 12, 24, and 48 h. Groups tested were white Portland cement (WPC), white Portland cement with zirconium oxide (WPCZO), and white mineral trioxide aggregate Angelus (MTA). Control group cells were not treated. The cytotoxicity was evaluated through mitochondrial-activity (MTT) and cell-density (crystal violet) assays. All cements showed low cytotoxicity. In general, at the concentration of 10 mg/mL there was an increase in viability of those groups treated with WPC and WPCZO when compared to the control group (p<0.05). A similar profile for the absorbance values was noted among the groups: 10 mg/mL presented an increase in viability compared to the control group. On the other hand, smaller concentrations presented a similar or lower viability compared to the control group, in general. A new dental material composed of calcium silicate-based cement with 20% zirconium oxide as the radiopacifier showed low cytotoxicity as a promising material to be exploited for root-end filling.

Singlet oxygen explicit dosimetry to predict long-term local tumor control for BPD-mediated photodynamic therapy

NASA Astrophysics Data System (ADS)

Kim, Michele M.; Penjweini, Rozhin; Ong, Yi Hong; Zhu, Timothy C.

2017-02-01

Photodynamic therapy (PDT) is a well-established treatment modality for cancer and other malignant diseases; however, quantities such as light fluence, photosensitizer photobleaching rate, and PDT dose do not fully account for all of the dynamic interactions between the key components involved. In particular, fluence rate (Φ) effects are not accounted for, which has a large effect on the oxygen consumption rate. In this preclinical study, reacted singlet oxygen [1O2]rx was investigated as a dosimetric quantity for PDT outcome. The ability of [1O2]rx to predict the long-term local tumor control rate (LCR) for BPD-mediated PDT was examined. Mice bearing radioactivelyinduced fibrosarcoma (RIF) tumors were treated with different in-air fluences (250, 300, and 350 J/cm2) and in-air ϕ (75, 100, and150 mW/cm2) with a BPD dose of 1 mg/kg and a drug-light interval of 3 hours. Treatment was delivered with a collimated laser beam of 1 cm diameter at 690 nm. Explicit dosimetry of initial tissue oxygen concentration, tissue optical properties, and BPD concentration was used to calculate [1O2]rx. Φ was calculated for the treatment volume based on Monte-Carlo simulations and measured tissue optical properties. Kaplan-Meier analyses for LCR were done for an endpoint of tumor volume <= 100 mm3 using four dose metrics: light fluence, photosensitizer photobleaching rate, PDT dose, and [1O2]rx. PDT dose was defined as the product of the timeintegral of photosensitizer concentration and Φ at a 3 mm tumor depth. Preliminary studies show that [1O2]rx better correlates with LCR and is an effective dosimetric quantity that can predict treatment outcome.

GPER1 mediates estrogen-induced neuroprotection against oxygen-glucose deprivation in the primary hippocampal neurons.

PubMed

Zhao, Tian-Zhi; Shi, Fei; Hu, Jun; He, Shi-Ming; Ding, Qian; Ma, Lian-Ting

2016-07-22

It is well-known that the neuroprotective effects of estrogen have potential in the prevention and amelioration of ischemic and degenerative neurological disorders, while the underlying mechanisms for estrogen actions are undefined. As an important mediator for the non-genomic functions of estrogen, GPER1 (G Protein-coupled Estrogen Receptor 1) has been suggested to involve in the beneficial roles of estrogen in neural cells. Here our studies on primary hippocampal neurons have focused on GPER1 in an in vitro model of ischemia using oxygen-glucose deprivation (OGD). GPER1 expression in the primary hippocampal neurons was stimulated by the OGD treatments. Both E2 (estradiol) and E2-BSA (membrane impermeable estradiol by covalent conjugation of bovine serum albumin) attenuated OGD-induced cell death in primary cultures of hippocampal neurons. Importantly, this membrane-mediated estrogen function requires GPER1 protein. Knocking down of GPER1 diminished, while overexpression of GPER1 potentiated, the protective roles of E2/E2-BSA following OGD. Additionally, the downstream mechanisms employed by membrane-associated estrogen signaling were found to include PI3K/Akt-dependent Ask1 inhibition in the primary hippocampal neurons. Overall, these research results could enhance our understanding of the neuroprotective actions for estrogen, and provide a new therapeutic target for improving stroke outcome and ameliorating degenerative neurological diseases. Copyright © 2016 IBRO. Published by Elsevier Ltd. All rights reserved.

Ciclopirox induces autophagy through reactive oxygen species-mediated activation of JNK signaling pathway

PubMed Central

Zhou, Hongyu; Shen, Tao; Shang, Chaowei; Luo, Yan; Liu, Lei; Yan, Juming; Li, Yan; Huang, Shile

2014-01-01

Ciclopirox olamine (CPX), a fungicide, has been demonstrated as a potential anticancer agent. However, the underlying anticancer mechanism is not well understood. Here, we found that CPX induced autophagy in human rhabdomyosarcoma (Rh30 and RD) cells. It appeared that CPX-induced autophagy was attributed to induction of reactive oxygen species (ROS), as N-acetyl-L-cysteine (NAC), a ROS scavenger and antioxidant, prevented this process. Furthermore, we observed that CPX induced activation of mitogen-activated protein kinases (MAPKs), including extracellular signal-regulated kinase 1/2 (ERK1/2), c-Jun N-terminal kinase (JNK) and p38 MAPK, which was also blocked by NAC. However, only inhibition of JNK (with SP600125) or expression of dominant negative c-Jun partially prevented CPX-induced autophagy, indicating that ROS-mediated activation of JNK signaling pathway contributed to CPX-induced autophagy. Of interest, inhibition of autophagy by chloroquine (CQ) enhanced CPX-induced cell death, indicating that CPX-induced autophagy plays a pro-survival role in human rhabdomyosarcoma cells. Our finding suggests that the combination with autophagy inhibitors may be a novel strategy in potentiating the anticancer activity of CPX for treatment of rhabdomyosarcoma. PMID:25294812

Zirconium Hydride Space Power Reactor design.

NASA Technical Reports Server (NTRS)

Asquith, J. G.; Mason, D. G.; Stamp, S.

1972-01-01

The Zirconium Hydride Space Power Reactor being designed and fabricated at Atomics International is intended for a wide range of potential applications. Throughout the program a series of reactor designs have been evaluated to establish the unique requirements imposed by coupling with various power conversion systems and for specific applications. Current design and development emphasis is upon a 100 kilowatt thermal reactor for application in a 5 kwe thermoelectric space power generating system, which is scheduled to be fabricated and ground tested in the mid 70s. The reactor design considerations reviewed in this paper will be discussed in the context of this 100 kwt reactor and a 300 kwt reactor previously designed for larger power demand applications.

METHOD FOR DISSOLVING ZIRCONIUM-URANIUM COMPOSITIONS

DOEpatents

Gens, T.A.

1961-07-18

A method is descrioed for treating a zirconium-- uranium composition to form a stable solution from which uranium and other values may be extracted by contacting the composition with at least a 4 molar aqueous solution of ammonium fluoride at a temperature of about 100 deg C, adding a peroxide, in incremental amounts, to the heated solution throughout the period of dissolution until all of the uranium is converted to soluble uranyl salt, adding nitric acid to the resultant solution to form a solvent extraction feed solution to convert the uranyl salt to a solvent extractable state, and thereafter recovering the uranium and other desired values from the feed solution by solvent extraction.

Cherenkov and Scintillation Properties of Cubic Zirconium

NASA Technical Reports Server (NTRS)

Christl, M.J.; Adams, J.H.; Parnell, T.A.; Kuznetsov, E.N.

2008-01-01

Cubic zirconium (CZ) is a high index of refraction (n =2.17) material that we have investigated for Cherenkov counter applications. Laboratory and proton accelerator tests of an 18cc sample of CZ show that the expected fast Cherenkov response is accompanied by a longer scintillation component that can be separated by pulse shaping. This presents the possibility of novel particle spectrometers which exploits both properties of CZ. Other high index materials being examined for Cherenkov applications will be discussed. Results from laboratory tests and an accelerator exposure will be presented and a potential application in solar energetic particle instruments will be discussed

Efficient mass-selective three-photon ionization of zirconium atoms

DOEpatents

Page, Ralph H.

1994-01-01

In an AVLIS process, .sup.91 Zr is selectively removed from natural zirconium by a three-step photoionization wherein Zr atoms are irradiated by a laser beam having a wavelength .lambda..sub.1, selectively raising .sup.91 Zr atoms to an odd-parity E.sub.1 energy level in the range of 16000-19000 cm.sup.-1, are irradiated by a laser beam having a wavelength .lambda..sub.2 to raise the atoms from an E.sub.l level to an even-parity E.sub.2 energy level in the range of 35000-37000 cm.sup.-1 and are irradiated by a laser beam having a wavelength .lambda..sub.3 to cause a resonant transition of atoms from an E.sub.2 level to an autoionizing level above 53506 cm.sup.-1. .lambda..sub.3 wavelengths of 5607, 6511 or 5756 .ANG. will excite a zirconium atom from an E.sub.2 energy state of 36344 cm.sup.-1 to an autoionizing level; a .lambda..sub.3 wavelength of 5666 .ANG. will cause an autoionizing transition from an E.sub.2 level of 36068 cm.sup.-1 ; and a .lambda. .sub.3 wavelength of 5662 .ANG. will cause an ionizing resonance of an atom at an E.sub.2 level of 35904 cm.sup.-1.

Copper mediated polymerization without external deoxygenation or oxygen scavengers.

PubMed

Liarou, Evelina; Whitfield, Richard; Anastasaki, Athina; Engelis, Nikolaos G; Jones, Glen R; Velonia, Kelly; Haddleton, David

2018-05-14

Overcoming the challenge of rigorous deoxygenation in copper mediated controlled radical polymerization processes (e.g. ATRP), we report a simple Cu(0)-RDRP system in the absence of external additives (e.g. reducing agents, enzymes etc.). By simply adjusting the headspace of the reaction vessel, a wide range of monomers, namely acrylates, methacrylates, acrylamides and styrene, can be polymerized in a controlled manner yielding polymers with low dispersities, near-quantitative conversions and high end group fidelity. Significantly, this approach is scalable (~ 125 g), tolerant to elevated temperatures, compatible with both organic and aqueous media and does not rely on external stimuli which may limit the monomer pool. The robustness and versatility of this methodology is further demonstrated by the applicability to a number of other copper mediated techniques including conventional ATRP and light-mediated approaches. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

OH radicals from the indirect actions of X-rays induce cell lethality and mediate the majority of the oxygen enhancement effect.

PubMed

Hirayama, Ryoichi; Ito, Atsushi; Noguchi, Miho; Matsumoto, Yoshitaka; Uzawa, Akiko; Kobashi, Gen; Okayasu, Ryuichi; Furusawa, Yoshiya

2013-11-01

We examined OH radical-mediated indirect actions from X irradiation on cell killing in wild-type Chinese hamster ovary cell lines (CHO and AA8) under oxic and hypoxic conditions, and compared the contribution of direct and indirect actions under both conditions. The contribution of indirect action on cell killing can be estimated from the maximum degree of protection by dimethylsulfoxide, which suppresses indirect action by quenching OH radicals without affecting the direct action of X rays on cell killing. The contributions of indirect action on cell killing of CHO cells were 76% and 50% under oxic and hypoxic conditions, respectively, and those for AA8 cells were 85% and 47%, respectively. Therefore, the indirect action on cell killing was enhanced by oxygen during X irradiation in both cell lines tested. Oxygen enhancement ratios (OERs) at the 10% survival level (D10 or LD90) for CHO and AA8 cells were 2.68 ± 0.15 and 2.76 ± 0.08, respectively. OERs were evaluated separately for indirect and direct actions, which gave the values of 3.75 and 2.01 for CHO, and 4.11 and 1.32 for AA8 cells, respectively. Thus the generally accepted OER value of ∼3 is best understood as the average of the OER values for both indirect and direct actions. These results imply that both indirect and direct actions on cell killing require oxygen for the majority of lethal DNA damage, however, oxygen plays a larger role in indirect than for direct effects. Conversely, the lethal damage induced by the direct action of X rays are less affected by oxygen concentration.

γ-Oryzanol suppresses COX-2 expression by inhibiting reactive oxygen species-mediated Erk1/2 and Egr-1 signaling in LPS-stimulated RAW264.7 macrophages.

PubMed

Shin, Soon Young; Kim, Heon-Woong; Jang, Hwan-Hee; Hwang, Yu-Jin; Choe, Jeong-Sook; Kim, Jung-Bong; Lim, Yoongho; Lee, Young Han

2017-09-16

Cyclooxygenase (COX)-2 produces prostanoids, which contribute to inflammatory responses. Nuclear factor (NF)-κB is a key transcription factor mediating COX-2 expression. γ-Oryzanol is an active component in rice bran oil, which inhibits lipopolysaccharide (LPS)-mediated COX-2 expression by inhibiting NF-κB. However, the inhibition of COX-2 expression by γ-oryzanol independently of NF-κB is poorly understood. We found that LPS upregulated Egr-1 expression at the transcriptional level. Forced expression of Egr-1 trans-activated the Cox-2 promoter independently of NF-κB. In contrast, silencing of Egr-1 abrogated LPS-mediated COX-2 expression. LPS produced reactive oxygen species (ROS), which, in turn, induced Egr-1 expression via the Erk1/2 MAPK pathway. ROS scavenging activity of γ-oryzanol suppressed Egr-1 expression by inhibiting the Erk1/2 MAPK pathway. Our results suggest that γ-oryzanol inhibits LPS-mediated COX-2 expression by suppressing Erk1/2-mediated Egr-1 expression. This study supports that γ-oryzanol may be useful for ameliorating LPS-mediated inflammatory responses. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of surface treatment and type of cement on push-out bond strength of zirconium oxide posts.

PubMed

Almufleh, Balqees S; Aleisa, Khalil I; Morgano, Steven M

2014-10-01

The effect of the surface treatment of zirconium oxide posts on their push-out bond strength is controversial. The purpose of this study was to compare the effects of 2 surface treatments on the bond strength of zirconium oxide posts cemented with different cements and to assess the failure mode. Seventy extracted human teeth were divided into 7 groups (n=10). Custom zirconium oxide posts (Cercon; Degudent) were fabricated for 6 groups. Posts in 3 groups were airborne-particle abraded (A). Posts in the other 3 groups were tribochemical silica coated (T). Three cements were used. Zinc phosphate cement was used to cement the zirconium oxide posts in groups AZ and TZ, RelyX ARC cement was used in groups ARA and TRA, and RelyX Unicem cement was used in groups ARU and TRU. Group C contained custom metal posts cemented with zinc phosphate cement. Specimens were horizontally sectioned into 3 sections and subjected to a push-out test. A mixed model analysis of variance, 1-way ANOVA, and the Tukey multiple comparison tests were used for statistical analysis. The highest push-out bond strength was recorded for Group ARU (21.03 MPa), and the lowest was recorded for Group ARA (7.57 MPa). No significant difference in push-out bond strength was found among the different surface treatments and root regions (P>.05). The type of cement had a significant effect on the push-out bond strength of zirconium oxide posts (P=.049). RelyX Unicem cement recorded (19.57 ±8.83 MPa) significantly higher push-out bond strength compared with zinc phosphate (9.95 ±6.31 MPa) and RelyX ARC cements (9.39 ±5.45 MPa). Adhesive failure at the post-cement interface was recorded for 75% of the posts cemented with zinc phosphate and RelyX ARC cements, while mixed failure was recorded for 75% of the posts cemented with RelyX Unicem cement. The type of cement used resulted in a statistically significant difference in the push-out bond strength of zirconium oxide posts, while both the surface treatment

21 CFR 700.16 - Use of aerosol cosmetic products containing zirconium.

Code of Federal Regulations, 2010 CFR

2010-04-01

... indicates that certain zirconium compounds have caused human skin granulomas and toxic effects in the lungs... deep portions of the lungs of users. The lung is an organ, like skin, subject to the development of granulomas. Unlike the skin, the lung will not reveal the presence of granulomatous changes until they have...

Reactive oxygen species mediate human hepatocyte injury during hypoxia/reoxygenation.

PubMed

Bhogal, Ricky Harminder; Curbishley, Stuart M; Weston, Christopher J; Adams, David H; Afford, Simon C

2010-11-01

Increasing evidence shows that reactive oxygen species (ROS) may be critical mediators of liver damage during the relative hypoxia of ischemia/reperfusion injury (IRI) associated with transplant surgery or of the tissue microenvironment created as a result of chronic hepatic inflammation or infection. Much work has been focused on Kupffer cells or liver resident macrophages with respect to the generation of ROS during IRI. However, little is known about the contribution of endogenous hepatocyte ROS production or its potential impact on the parenchymal cell death associated with IRI and chronic hepatic inflammation. For the first time, we show that human hepatocytes isolated from nondiseased liver tissue and human hepatocytes isolated from diseased liver tissue exhibit marked differences in ROS production in response to hypoxia/reoxygenation (H-R). Furthermore, several different antioxidants are able to abrogate hepatocyte ROS-induced cell death during hypoxia and H-R. These data provide clear evidence that endogenous ROS production by mitochondria and nicotinamide adenine dinucleotide phosphate oxidase drives human hepatocyte apoptosis and necrosis during hypoxia and H-R and may therefore play an important role in any hepatic diseases characterized by a relatively hypoxic liver microenvironment. In conclusion, these data strongly suggest that hepatocytes and hepatocyte-derived ROS are active participants driving hepatic inflammation. These novel findings highlight important functional/metabolic differences between hepatocytes isolated from normal donor livers, hepatocytes isolated from normal resected tissue obtained during surgery for malignant neoplasms, and hepatocytes isolated from livers with end-stage disease. Furthermore, the targeting of hepatocyte ROS generation with antioxidants may offer therapeutic potential for the adjunctive treatment of IRI and chronic inflammatory liver diseases. © 2010 AASLD.

Fabrication of oxide layer on zirconium by micro-arc oxidation: Structural and antimicrobial characteristics.

PubMed

Fidan, S; Muhaffel, F; Riool, M; Cempura, G; de Boer, L; Zaat, S A J; Filemonowicz, A Czyrska-; Cimenoglu, H

2017-02-01

The aim of this study was to cover the surfaces of zirconium (Zr) with an antimicrobial layer for biomedical applications. For this purpose, the micro-arc oxidation (MAO) process was employed in a sodium silicate and sodium hydroxide containing base electrolyte with and without addition of silver acetate (AgC 2 H 3 O 2 ). In general, synthesized MAO layers were composed of zirconium oxide (ZrO 2 ) and zircon (ZrSiO 4 ). Addition of AgC 2 H 3 O 2 into the base electrolyte caused homogenous precipitation of silver-containing particles in the MAO layer, which exhibited excellent antibacterial efficiency against methicillin-resistant Staphylococcus aureus (MRSA) as compared to the untreated and MAO-treated Zr. Copyright © 2016 Elsevier B.V. All rights reserved.

REACTIVE OXYGEN SPECIES: IMPACT ON SKELETAL MUSCLE

PubMed Central

Powers, Scott K.; Ji, Li Li; Kavazis, Andreas N.; Jackson, Malcolm J.

2014-01-01

It is well established that contracting muscles produce both reactive oxygen and nitrogen species. Although the sources of oxidant production during exercise continue to be debated, growing evidence suggests that mitochondria are not the dominant source. Regardless of the sources of oxidants in contracting muscles, intense and prolonged exercise can result in oxidative damage to both proteins and lipids in the contracting myocytes. Further, oxidants regulate numerous cell signaling pathways and modulate the expression of many genes. This oxidant-mediated change in gene expression involves changes at transcriptional, mRNA stability, and signal transduction levels. Furthermore, numerous products associated with oxidant-modulated genes have been identified and include antioxidant enzymes, stress proteins, and mitochondrial electron transport proteins. Interestingly, low and physiological levels of reactive oxygen species are required for normal force production in skeletal muscle, but high levels of reactive oxygen species result in contractile dysfunction and fatigue. Ongoing research continues to explore the redox-sensitive targets in muscle that are responsible for both redox-regulation of muscle adaptation and oxidant-mediated muscle fatigue. PMID:23737208

Influence of growth temperature on properties of zirconium dioxide films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Kukli, Kaupo; Ritala, Mikko; Aarik, Jaan; Uustare, Teet; Leskela, Markku

2002-08-01

ZrO2 films were grown by atomic layer deposition from ZrCl4 and H2O or a mixture of H2O and H2O2 on Si(100) substrates in the temperature range of 180-600 degC. The films were evaluated in the as-deposited state, in order to follow the effect of deposition temperature on the film quality. The rate of crystal growth increased and the content of residual impurities decreased with increasing temperature. The zirconium-to-oxygen atomic ratio, determined by ion-beam analysis, corresponded to the stoichiometric dioxide regardless of the growth temperature. The effective permittivity of ZrO2 in Al/ZrO2/Si capacitor structures increased from 13-15 in the films grown at 180 degC to 19 in the films grown at 300-600 degC, measured at 100 kHz. The permittivity was relatively high in the crystallized films, compared to the amorphous ones, but rather insensitive to the crystal structure. The permittivity was higher in the films grown using water. The leakage current density tended to be lower and the breakdown field higher in the films grown using hydrogen peroxide.

Effects of alpha-zirconium phosphate on thermal degradation and flame retardancy of transparent intumescent fire protective coating

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

Xing, Weiyi; Zhang, Ping; Song, Lei

2014-01-01

Graphical abstract: - Highlights: • A transparent intumescent fire protective coating was obtained by UV-cured technology. • OZrP could enhance the thermal stability and anti-oxidation of the coating. • OZrP could reduce the combustion properties of the coatings. - Abstract: Organophilic alpha-zirconium phosphate (OZrP) was used to improve the thermal and fire retardant behaviors of the phenyl di(acryloyloxyethyl)phosphate (PDHA)-triglycidyl isocyanurate acrylate (TGICA)-2-phenoxyethyl acrylate (PHEA) (PDHA-TGICA-PHEA) coating. The morphology of nanocomposite coating was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of OZrP on the flame retardancy, thermal stability, fireproofing time and char formation of the coatingsmore » was investigated by microscale combustion calorimeter (MCC), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), laser Raman spectroscopy (LRS) and scanning electric microscope (SEM). The results showed that by adding OZrP, the peak heat release rate and total heat of combustion were significantly reduced. The highest improvement was achieved with 0.5 wt% OZrP. XPS analysis indicated that the performance of anti-oxidation of the coating was improved with the addition of OZrP, and SEM images showed that a good synergistic effect was obtained through a ceramic-like layer produced by OZrP covered on the surface of char.« less

SEPARATION OF POLONIUM, PROTACTINIUM OR MIXTURES THEREOF IN AQUEOUS SOLUTION FROM BISMUTH, LEAD, ZIRCONIUM AND/OR COLUMBIUM VALUES

DOEpatents

Van Winkle, Q.; Kraus, K.A.

1959-10-27

A process is presented for separating polonium, protactinium, or mixtures thereof in aqueous solution from bismuth, zirconium, lead, and niobium values contained in the solution. The method comprises providing hydrochloric acid in the solution in a concentration of at least 5N. contacting the aqueous solution with a substantially waterimmiscible organic solvent such as diisopropyl ketone, and separating the aqueous phase containing the bismuth, zirconium, lead, and niobium from the organic extract phase containing the polonium, protactinium, or mixture thereof.

Dioxygen in Polyoxometalate Mediated Reactions.

PubMed

Weinstock, Ira A; Schreiber, Roy E; Neumann, Ronny

2018-03-14

In this review article, we consider the use of molecular oxygen in reactions mediated by polyoxometalates. Polyoxometalates are anionic metal oxide clusters of a variety of structures that are soluble in liquid phases and therefore amenable to homogeneous catalytic transformations. Often, they are active for electron transfer oxidations of a myriad of substrates and upon reduction can be reoxidized by molecular oxygen. For example, the phosphovanadomolybdate, H 5 PV 2 Mo 10 O 40 , can oxidize Pd(0) thereby enabling aerobic reactions catalyzed by Pd and H 5 PV 2 Mo 10 O 40 . In a similar vein, polyoxometalates can stabilize metal nanoparticles, leading to additional transformations. Furthermore, electron transfer oxidation of other substrates such as halides and sulfur-containing compounds is possible. More uniquely, H 5 PV 2 Mo 10 O 40 and its analogues can mediate electron transfer-oxygen transfer reactions where oxygen atoms are transferred from the polyoxometalate to the substrate. This unique property has enabled correspondingly unique transformations involving carbon-carbon, carbon-hydrogen, and carbon-metal bond activation. The pathway for the reoxidation of vanadomolybdates with O 2 appears to be an inner-sphere reaction, but the oxidation of one-electron reduced polyoxotungstates has been shown through intensive research to be an outer-sphere reaction. Beyond electron transfer and electron transfer-oxygen transfer aerobic transformations, there a few examples of apparent dioxygenase activity where both oxygen atoms are donated to a substrate.

Extending FEAST-METAL for analysis of low content minor actinide bearing and zirconium rich metallic fuels for sodium fast reactors

NASA Astrophysics Data System (ADS)

Karahan, Aydın

2011-07-01

Computational models in FEAST-METAL fuel behaviour code have been upgraded to simulate minor actinide bearing zirconium rich metallic fuels for use in sodium fast reactors. Increasing the zirconium content to 20-40 wt.% causes significant changes in fuel slug microstructure affecting thermal, mechanical, chemical, and fission gas behaviour. Inclusion of zirconium rich phase reduces the fission gas swelling rate significantly in early irradiation. Above the threshold fission gas swelling, formation of micro-cracks, and open pores increase material compliancy enhance diffusivity, leading to rapid fuel gas swelling, interconnected porosity development and release of the fission gases and helium. Production and release of helium was modelled empirically as a function of americium content and fission gas production, consistent with previous Idaho National Laboratory studies. Predicted fuel constituent redistribution is much smaller compared to typical U-Pu-10Zr fuel operated at EBR-II. Material properties such as fuel thermal conductivity, modulus of elasticity, and thermal expansion coefficient have been approximated using the available database. Creep rate and fission gas diffusivity of high zirconium fuel is lowered by an order of magnitude with respect to the reference low zirconium fuel based on limited database and in order to match experimental observations. The new code is benchmarked against the AFC-1F fuel assembly post irradiation examination results. Satisfactory match was obtained for fission gas release and swelling behaviour. Finally, the study considers a comparison of fuel behaviour between high zirconium content minor actinide bearing fuel and typical U-15Pu-6Zr fuel pins with 75% smear density. The new fuel has much higher fissile content, allowing for operating at lower neutron flux level compared to fuel with lower fissile density. This feature allows the designer to reach a much higher burnup before reaching the cladding dose limit. On the other

Zirconium doped TiO{sub 2} thin films: A promising dielectric layer

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

Kumar, Arvind; Mondal, Sandip, E-mail: sandipmondal@physics.iisc.ernet.in; Rao, K. S. R. Koteswara

2016-05-06

In the present work, we have fabricated the zirconium doped TiO{sub 2} thin (ZTO) films from a facile spin – coating method. The addition of Zirconium in TiO{sub 2} offers conduction band offset to Si and consequently decreased the leakage current density by approximately two orders as compared to pure TiO{sub 2} thin (TO) films. The ZTO thin film shows a high dielectric constant 27 with a very low leakage current density ∼10{sup −8} A/cm{sup 2}. The oxide capacitate, flat band voltage and change in flat band voltage are 172 pF, -1.19 V and 54 mV. The AFM analysis confirmed the compactmore » and pore free flat surface. The RMS surface roughness is found to be 1.5 Å. The ellipsometry analysis also verified the fact with a high refractive index 2.21.« less

Oxygen radicals as key mediators in neurological disease: fact or fiction?

PubMed

Halliwell, B

1992-01-01

A free radical is any species capable of independent existence that contains one or more unpaired electrons. Free radicals and other reactive oxygen species are frequently proposed to be involved in the pathology of several neurological disorders. Criteria for establishing such involvement are presented. Development of new methods for measuring oxidative damage should enable elucidation of the precise role of reactive oxygen species in neurological disorders.

METHOD FOR ANNEALING AND ROLLING ZIRCONIUM-BASE ALLOYS

DOEpatents

Picklesimer, M.L.

1959-07-14

A fabrication procedure is presented for alpha-stabilized zirconium-base alloys, and in particular Zircaloy-2. The alloy is initially worked at a temperature outside the alpha-plus-beta range (810 to 970 deg ), held at a temperature above 970 deg C for 30 minutes and cooled rapidly. The alloy is then cold-worked to reduce the size at least 20% and annealed at a temperature from 700 to 810 deg C. This procedure serves both to prevent the formation of stringers and to provide a randomly oriented crystal structure.

Dissolved oxygen: Chapter 6

USGS Publications Warehouse

Senn, David; Downing-Kunz, Maureen; Novick, Emily

2016-01-01

Dissolved oxygen (DO) concentration serves as an important indicator of estuarine habitat condition, because all aquatic macro-organisms require some minimum DO level to survive and prosper. The instantaneous DO concentration, measured at a specific location in the water column, results from a balance between multiple processes that add or remove oxygen (Figure 6.1): primary production produces O2; aerobic respiration in the water column and sediments consumes O2; abiotic or microbially-mediated biogeochemical reactions utilize O2 as an oxidant (e.g., oxidation of ammonium, sulfide, and ferrous iron); O2 exchange occurs across the air:water interface in response to under- or oversaturated DO concentrations in the water column; and water currents and turbulent mixing transport DO into and out of zones in the water column. If the oxygen loss rate exceeds the oxygen production or input rate, DO concentration decreases. When DO losses exceed production or input over a prolonged enough period of time, hypoxia ((<2-3 mg/L) or anoxia can develop. Persistent hypoxia or anoxia causes stress or death in aquatic organism populations, or for organisms that can escape a hypoxic or anoxic area, the loss of habitat. In addition, sulfide, which is toxic to aquatic organisms and causes odor problems, escapes from sediments under low oxygen conditions. Low dissolved oxygen is a common aquatic ecosystem response to elevated organic

Amperometric Biosensor Based on Zirconium Oxide/Polyethylene Glycol/Tyrosinase Composite Film for the Detection of Phenolic Compounds

PubMed Central

Ahmad, Nor Monica; Abdullah, Jaafar; Yusof, Nor Azah; Ab Rashid, Ahmad Hazri; Abd Rahman, Samsulida; Hasan, Md. Rakibul

2016-01-01

A phenolic biosensor based on a zirconium oxide/polyethylene glycol/tyrosinase composite film for the detection of phenolic compounds has been explored. The formation of the composite film was expected via electrostatic interaction between hexacetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), and zirconium oxide nanoparticles casted on screen printed carbon electrode (SPCE). Herein, the electrode was treated by casting hexacetyltrimethylammonium bromide on SPCE to promote a positively charged surface. Later, zirconium oxide was mixed with polyethylene glycol and the mixture was dropped cast onto the positively charged SPCE/CTAB. Tyrosinase was further immobilized onto the modified SPCE. Characterization of the prepared nanocomposite film and the modified SPCE surface was investigated by scanning electron microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), and Cyclic voltamogram (CV). The developed biosensor exhibits rapid response for less than 10 s. Two linear calibration curves towards phenol in the concentrations ranges of 0.075–10 µM and 10–55 µM with the detection limit of 0.034 µM were obtained. The biosensor shows high sensitivity and good storage stability for at least 30 days. PMID:27367738

Amperometric Biosensor Based on Zirconium Oxide/Polyethylene Glycol/Tyrosinase Composite Film for the Detection of Phenolic Compounds.

PubMed

Ahmad, Nor Monica; Abdullah, Jaafar; Yusof, Nor Azah; Ab Rashid, Ahmad Hazri; Abd Rahman, Samsulida; Hasan, Md Rakibul

2016-06-29

A phenolic biosensor based on a zirconium oxide/polyethylene glycol/tyrosinase composite film for the detection of phenolic compounds has been explored. The formation of the composite film was expected via electrostatic interaction between hexacetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), and zirconium oxide nanoparticles casted on screen printed carbon electrode (SPCE). Herein, the electrode was treated by casting hexacetyltrimethylammonium bromide on SPCE to promote a positively charged surface. Later, zirconium oxide was mixed with polyethylene glycol and the mixture was dropped cast onto the positively charged SPCE/CTAB. Tyrosinase was further immobilized onto the modified SPCE. Characterization of the prepared nanocomposite film and the modified SPCE surface was investigated by scanning electron microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), and Cyclic voltamogram (CV). The developed biosensor exhibits rapid response for less than 10 s. Two linear calibration curves towards phenol in the concentrations ranges of 0.075-10 µM and 10-55 µM with the detection limit of 0.034 µM were obtained. The biosensor shows high sensitivity and good storage stability for at least 30 days.

In vitro and in vivo characterization of anodised zirconium as a potential material for biomedical applications.

PubMed

Katunar, Maria R; Gomez Sanchez, Andrea; Santos Coquillat, Ana; Civantos, Ana; Martinez Campos, Enrique; Ballarre, Josefina; Vico, Tamara; Baca, Matias; Ramos, Viviana; Cere, Silvia

2017-06-01

In vitro studies offer the insights for the understanding of the mechanisms at the tissue-implant interface that will provide an effective functioning in vivo. The good biocompatibility of zirconium makes a good candidate for biomedical applications and the attractive in vivo performance is mainly due to the presence of a protective oxide layer. The aim of this study is to evaluate by in vitro and in vivo approach, the influence of surface modification achieved by anodisation at 30 and 60V on zirconium implants on the first steps of the osseointegration process. In this study cell attachment, proliferation and morphology of mouse myoblast C2C12-GFP and in mouse osteoprogenitor MC3T3-E1 cells was evaluated. Also, together with the immune system response, osteoclast differentiation and morphology with RAW 264.7 murine cell line were analysed. It was found that anodisation treatment at 60V enhanced cell spreading and the osteoblastic and osteoclastic cells morphology, showing a strong dependence on the surface characteristics. In vivo tests were performed in a rat femur osteotomy model. Dynamical and static histological and histomorphometric analyses were developed 15 and 30days after surgery. Newly formed bone around Zr60V implants showed a continuous newly compact and homogeneous bone just 15 after surgery, as judged by the enhanced thickness and mineralization rate. The results indicate that anodising treatment at 60V could be an effective improvement in the osseointegration of zirconium by stimulating adhesion, proliferation, morphology, new bone thickness and bone mineral apposition, making zirconium an emerging candidate material for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

IMPACT OF OXYGEN MEDIATED OXIDATIVE COUPLING ON ADSORPTION KINETICS

EPA Science Inventory

The presence of molecular oxygen in the test environment promotes oxidative coupling (polymer formation) of phenolic compounds on the surface of granular activated carbon (GAC). Both adsorption equilibria and adsorption kinetics are affected by these chemical reactions. Lack of...

Singlet oxygen detection in biological systems: Uses and limitations

PubMed Central

Koh, Eugene; Fluhr, Robert

2016-01-01

ABSTRACT The study of singlet oxygen in biological systems is challenging in many ways. Singlet oxygen is a relatively unstable ephemeral molecule, and its properties make it highly reactive with many biomolecules, making it difficult to quantify accurately. Several methods have been developed to study this elusive molecule, but most studies thus far have focused on those conditions that produce relatively large amounts of singlet oxygen. However, the need for more sensitive methods is required as one begins to explore the levels of singlet oxygen required in signaling and regulatory processes. Here we discuss the various methods used in the study of singlet oxygen, and outline their uses and limitations. PMID:27231787

Curcumin induces ER stress-mediated apoptosis through selective generation of reactive oxygen species in cervical cancer cells.

PubMed

Kim, Boyun; Kim, Hee Seung; Jung, Eun-Ji; Lee, Jung Yun; K Tsang, Benjamin; Lim, Jeong Mook; Song, Yong Sang

2016-05-01

Prolonged accumulation of misfolded or unfolded proteins caused by cellular stress, including oxidative stress, induces endoplasmic reticulum stress, which then activates an unfolded protein response (UPR). ER stress is usually maintained at higher levels in cancer cells as compared to normal cells due to altered metabolism in cancer. Here, we investigated whether curcumin is ER stress-mediated apoptosis in cervical cancer cells, and ROS increased by curcumin are involved in the process as an upstream contributor. Curcumin inhibited proliferation of cervical cancer cells (C33A, CaSki, HeLa, and ME180) and induced apoptotic cell death. Curcumin activated ER-resident UPR sensors, such as PERK, IRE-1α, and ATF6, and their downstream-signaling proteins in cervical cancer cells, but not in normal epithelial cells and peripheral blood mononuclear cells (PBMCs). CHOP, a key factor involved in ER stress-mediated apoptosis, was also activated by curcumin. CHOP decreased the ratio of anti-apoptotic protein Bcl-2 to pro-apoptotic protein Bax expression, and subsequently increased the apoptotic population of cervical cancer cells. Furthermore, curcumin elevated levels of intracellular reactive oxygen species (ROS) in cervical cancer cells, but not in normal epithelial cells. Scavenging ROS resulted in inhibition of ER stress and partially restored cell viability in curcumin-treated cancer cells. Collectively, these observations show that curcumin promotes ER stress-mediated apoptosis in cervical cancer cells through increase of cell type-specific ROS generation. Therefore, modulation of these differential responses to curcumin between normal and cervical cancer cells could be an effective therapeutic strategy without adverse effects on normal cells. © 2015 Wiley Periodicals, Inc.

Study on the effect of reactive oxygen species-mediated oxidative stress on the activation of mitochondrial apoptosis and the tenderness of yak meat.

PubMed

Wang, Lin-Lin; Yu, Qun-Li; Han, Ling; Ma, Xiu-Li; Song, Ren-De; Zhao, Suo-Nan; Zhang, Wen-Hua

2018-04-01

This study investigated the effect of reactive oxygen species-mediated oxidative stress on activation of mitochondrial apoptosis and tenderness of yak meat during postmortem ageing. Oxidative stress degree, Ca 2+ levels, membrane permeability transition pore opening, mitochondrial membrane potential, apoptotic factors and the shear force were examined. Results showed that the ROS generated by H 2 O 2 significantly increased mitochondrial oxidative stress by decreasing the activities of superoxide dismutase, catalase and glutathione peroxidase, and increasing lipid peroxidation. Furthermore, oxidative stress enhanced Ca 2+ production and cytochrome c release, changed the levels of Bcl-2 family proteins and activated caspase-9 and -3 activities. Ultimately, oxidative stress increased the apoptosis rate and tenderness of yak meat. These observations confirmed that ROS-mediated oxidative stress participates in the activation of the apoptotic cascade reaction involving Ca 2+ and Bcl-2 family proteins. The results further suggested that ROS-mediated oxidative stress plays a significant role in meat tenderization through the mitochondrial apoptotic pathway. Copyright © 2017. Published by Elsevier Ltd.

Effect of oxygen at high pressure on spontaneous transmitter release.

PubMed

Colton, J S; Colton, C A

1978-11-01

The effect of oxygen at high pressure (OHP) on resting membrane properties (effective membrane resistance (Reff) and membrane potential (Vm)) and the spontaneous release of excitatory transmitter were examined at the lobster neuromuscular junction. Pressurization with 100% oxygen to 150 pounds per square inch gauge pressure (psig) or with nitrogen to 150 psig (7,000 mmHg nitrogen and 135 mmHg oxygen) produced a decrease in Reff associated with a hyperpolarization of Vm. These changes, however, returned to control values within 20--30 min after completion of pressurization. Spontaneous release of excitatory transmitter was shown to increase dramatically in the presence of 100% oxygen at 150 psig. The increase in miniature end-plate potential (MEPP) frequency persisted beyond the transient changes seen with Reff and Vm. This effect was selective to oxygen, as pressurization with nitrogen did not produce an increase in MEPP frequency. No change in average MEPP amplitude was seen with either OHP or pressure alone. An OHP-induced increase in MEPP frequency was also seen at the frog neuromuscular junction. The results indicate that both glutamate-mediated and acetylcholine-mediated synaptic transmission are altered by OHP.

Development of mediator-type biosensor to wirelessly monitor whole cholesterol concentration in fish.

PubMed

Takase, Mai; Murata, Masataka; Hibi, Kyoko; Huifeng, Ren; Endo, Hideaki

2014-04-01

We developed a wireless monitoring system to monitor fish condition by tracking the change in whole cholesterol concentration. The whole cholesterol concentration of fish is a source of steroid hormones or indicator of immunity level, which makes its detection important for tracking physiological condition of fish. Wireless monitoring system comprises of mediator-type biosensor and wireless transmission device. Biosensor is implantable to fish body, and transmission device is so light, in that fish is allowed to swim freely during monitoring. Cholesterol esterase and oxidase were fixated on to the detection site of biosensor and used to detect the whole cholesterol concentration. However, cholesterol oxidase incorporates oxidation-reduction reaction of oxygen for detection, which concentration fluctuates easily due to change in environmental condition. Meanwhile, mediator-type biosensor enables monitoring of whole cholesterol concentration by using mediator to substitute that oxidation-reduction reaction of oxygen. Characteristic of fabricated mediator-type biosensor was tested. The sensor output current of mediator-type biosensor remained stable compared to output current of non-mediator-type biosensor under fluctuating oxygen concentration of 0-8 ppm, which implied that this sensor is less affected by change in dissolved oxygen concentration. That biosensor was then implanted into fish for wireless monitoring. As a result, approximately 48 h of real-time monitoring was successful.

Oxygen Passivation Mediated Tunability of Trion and Excitons in MoS2

NASA Astrophysics Data System (ADS)

Gogoi, Pranjal Kumar; Hu, Zhenliang; Wang, Qixing; Carvalho, Alexandra; Schmidt, Daniel; Yin, Xinmao; Chang, Yung-Huang; Li, Lain-Jong; Sow, Chorng Haur; Neto, A. H. Castro; Breese, Mark B. H.; Rusydi, Andrivo; Wee, Andrew T. S.

2017-08-01

Using wide spectral range in situ spectroscopic ellipsometry with systematic ultrahigh vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS2 isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A (1.92 eV) and B (2.02 eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure. This tunability of the excitonic effects is likely due to passivation and reemergence of the gap states in the band structure during oxygen adsorption and desorption, respectively, as indicated by ab initio density functional theory calculation results. This Letter unravels and emphasizes the important role of adsorbed oxygen in the optical spectra and many-body interactions of MoS2 .

Retention of zirconium oxide ceramic crowns with three types of cement.

PubMed

Palacios, Rosario P; Johnson, Glen H; Phillips, Keith M; Raigrodski, Ariel J

2006-08-01

Information about the retentive strength of luting agents for zirconium oxide-based crowns is limited. It is unknown if this type of high-strength ceramic restoration requires adhesive cementation to enhance retention. The purpose of this in vitro study was to determine the ability of selected luting agents to retain a representative zirconium oxide ceramic crown under clinically simulated conditions. Recently extracted human molars were prepared with a flat occlusal surface, 20-degree taper, and approximately 4-mm axial length. The axial and occlusal surface areas were determined, and specimens were distributed equally by total surface area into 3 cementation groups (n=12). Zirconium oxide ceramic copings (Procera AllZirkon) with an occlusal bar to facilitate removal were fabricated using computer-aided design/computer-assisted manufacturing (CAD/CAM) technology. All copings were airborne-particle abraded with 50-mum Al(2)O(3) and then cleaned in an ultrasonic bath with isopropyl alcohol. Provisional cement was removed from the prepared teeth, followed by a pumice prophy. After trial insertion, the copings were cleaned with phosphoric acid, rinsed, dried, and dehydrated with isopropyl alcohol. They were then cemented with a seating force of 10 kg per tooth, using either a composite resin cement with adhesive agent (Panavia F 2.0 and ED Primer A & B [PAN]), a resin-modified glass ionomer cement (Rely X Luting [RXL]), or a self-adhesive modified composite resin (Rely X Unicem [RXU]). The cemented copings were thermal cycled at 5 degrees C and 55 degrees C for 5000 cycles with a 15 second dwell time, and then removed along the path of insertion using a universal testing machine at 0.5 mm/min. The removal force was recorded, and the stress of dislodgement was calculated using the surface area of each preparation. A 1-way analysis of variance was used to analyze the data (alpha=.05). The nature of failure was also recorded. Mean dislodgement stresses were 5.1, 6.1, and

Reactive Oxygen Species/Hypoxia-Inducible Factor-1α/Platelet-Derived Growth Factor-BB Autocrine Loop Contributes to Cocaine-Mediated Alveolar Epithelial Barrier Damage

PubMed Central

Yang, Lu; Chen, Xufeng; Simet, Samantha M.; Hu, Guoku; Cai, Yu; Niu, Fang; Kook, Yeonhee

2016-01-01

Abuse of psychostimulants, such as cocaine, has been shown to be closely associated with complications of the lung, such as pulmonary hypertension, edema, increased inflammation, and infection. However, the mechanism by which cocaine mediates impairment of alveolar epithelial barrier integrity that underlies various pulmonary complications has not been well determined. Herein, we investigate the role of cocaine in disrupting the alveolar epithelial barrier function and the associated signaling cascade. Using the combinatorial electric cell–substrate impedance sensing and FITC-dextran permeability assays, we demonstrated cocaine-mediated disruption of the alveolar epithelial barrier, as evidenced by increased epithelial monolayer permeability with a concomitant loss of the tight junction protein zonula occludens-1 (Zo-1) in both mouse primary alveolar epithelial cells and the alveolar epithelial cell line, L2 cells. To dissect the signaling pathways involved in this process, we demonstrated that cocaine-mediated induction of permeability factors, platelet-derived growth factor (PDGF-BB) and vascular endothelial growth factor, involved reactive oxygen species (ROS)-dependent induction of hypoxia-inducible factor (HIF)-1α. Interestingly, we demonstrated that ROS-dependent induction of another transcription factor, nuclear factor erythroid-2–related factor-2, that did not play a role in cocaine-mediated barrier dysfunction. Importantly, this study identifies, for the first time, that ROS/HIF-1α/PDGF-BB autocrine loop contributes to cocaine-mediated barrier disruption via amplification of oxidative stress and downstream signaling. Corroboration of these cell culture findings in vivo demonstrated increased permeability of the alveolar epithelial barrier, loss of expression of Zo-1, and a concomitantly increased expression of both HIF-1α and PDGF-BB. Pharmacological blocking of HIF-1α significantly abrogated cocaine-mediated loss of Zo-1. Understanding the

Efficient mass-selective three-photon ionization of zirconium atoms

DOEpatents

Page, R.H.

1994-12-27

In an AVLIS process, [sup 91]Zr is selectively removed from natural zirconium by a three-step photoionization wherein Zr atoms are irradiated by a laser beam having a wavelength [lambda][sub 1], selectively raising [sup 91]Zr atoms to an odd-parity E[sub 1] energy level in the range of 16000--19000 cm[sup [minus]1], are irradiated by a laser beam having a wavelength [lambda][sub 2] to raise the atoms from an E[sub l] level to an even-parity E[sub 2] energy level in the range of 35000--37000 cm[sup [minus]1] and are irradiated by a laser beam having a wavelength [lambda][sub 3] to cause a resonant transition of atoms from an E[sub 2] level to an autoionizing level above 53506 cm[sup [minus]1][lambda][sub 3] wavelengths of 5607, 6511 or 5756 [angstrom] will excite a zirconium atom from an E[sub 2] energy state of 36344 cm[sup [minus]1] to an autoionizing level; a [lambda][sub 3] wavelength of 5666 [angstrom] will cause an autoionizing transition from an E[sub 2] level of 36068 cm[sup [minus]1]; and a [lambda][sub 3] wavelength of 5662 [angstrom] will cause an ionizing resonance of an atom at an E[sub 2] level of 35904 cm[sup [minus]1]. 4 figures.

Zirconium: The material of the future in modern implantology.

PubMed

Kubasiewicz-Ross, Paweł; Dominiak, Marzena; Gedrange, Tomasz; Botzenhart, Ute U

2017-01-01

The authors present the contemporary state of knowledge concerning alternative materials for dental implantology. First of all, factors influencing osseointegration are stated. The most important factors seem to be the type of implant surface. Among the numerous parameters describing them, the most important are: average roughness and porous density. Some studies proved that materials with comparable surface roughness provide similar osseointegration. In modern implantology titanium is the material still considered as a "gold standard". However, aesthetic features of titanium still bear several disadvantages, especially in the case of periodontium with a thin biotype in the anterior, aesthetic sensitive area of the jaw. If a titanium implant is used in such a case, the mucosa at the implant's neck may become grayish and, consequently limits the success of the overall treatment. That was the reason for seeking alternative materials to manufacture dental implants. Initiated by general medicine, mainly orthopedics, the search led to the discovery of zirconium dioxide used in dental implantology. A small number of complications, good chemical parameters, anticorrosion, mechanical strength, elasticity module close to the one of steel, and especially biocompatibility made zirconium a perfect material for this purpose, although this material presents several problems in achieving optimal roughness. In this overview one of the probable methods, a process of partial synterization, is presented.

Characterization of deformation mechanisms in zirconium alloys: effect of temperature and irradiation

NASA Astrophysics Data System (ADS)

Long, Fei

Zirconium alloys have been widely used in the CANDU (CANada Deuterium Uranium) reactor as core structural materials. Alloy such as Zircaloy-2 has been used for calandria tubes; fuel cladding; the pressure tube is manufactured from alloy Zr-2.5Nb. During in-reactor service, these alloys are exposed to a high flux of fast neutron at elevated temperatures. It is important to understand the effect of temperature and irradiation on the deformation mechanism of zirconium alloys. Aiming to provide experimental guidance for future modeling predictions on the properties of zirconium alloys this thesis describes the result of an investigation of the change of slip and twinning modes in Zircaloy-2 and Zr-2.5Nb as a function of temperature and irradiation. The aim is to provide scientific fundamentals and experimental evidences for future industry modeling in processing technique design, and in-reactor property change prediction of zirconium components. In situ neutron diffraction mechanical tests carried out on alloy Zircaloy-2 at three temperatures: 100¢ªC, 300¢ªC, and 500¢ªC, and described in Chapter 3. The evolution of the lattice strain of individual grain families in the loading and Poisson's directions during deformation, which probes the operation of slip and twinning modes at different stress levels, are described. By using the same type of in situ neutron diffraction technique, tests on Zr-2.5Nb pressure tube material samples, in either the fast-neutron irradiated or un-irradiated condition, are reported in Chapter 4. In Chapter 5, the measurement of dislocation density by means of line profile analysis of neutron diffraction patterns, as well as TEM observations of the dislocation microstructural evolution, is described. In Chapter 6 a hot-rolled Zr-2.5Nb with a larger grain size compared with the pressure tubing was used to study the development of dislocation microstructures with increasing plastic strain. In Chapter 7, in situ loading of heavy ion

Hyperglycemia-induced mouse trophoblast spreading is mediated by reactive oxygen species.

PubMed

Sánchez-Santos, Alejandra; Martínez-Hernández, María G; Contreras-Ramos, Alejandra; Ortega-Camarillo, Clara; Baiza-Gutman, Luis A

2018-04-01

During embryo implantation, the outer layer of the blastocyst interacts with the endometrium giving rise to the development of the trophoblast cell lineage. The cells in this lineage participate in the penetration of endometrium due to their motility and invasive properties. The mechanisms that regulate the differentiation and invasive ability of these cells are essential for the establishment and maintenance of an efficient exchange between maternal and fetal tissues during pregnancy. In this context, hyperglycemia can induce oxidative stress causing alterations in the placenta. This study evaluated the role of reactive oxygen species (ROS) in the actions of high glucose concentration (HG) on trophoblast spreading and the expression of extracellular proteases in cultured mouse conceptuses. Blastocysts from gestational day 4 (GD4) were cultured until GD7 in HAM-F10 medium and further treated for 48 hr with HG (25 mM glucose) from GD7 to GD9. This treatment induced larger trophoblast outgrowths and increased ROS concentration, which was associated with increased expression levels of urokinase-type plasminogen activator (PLAU), plasminogen activator inhibitor 1 (PAI-1), and matrix metalloproteinase 9 (MMP-9). These effects were prevented by treatment with the non-specific antioxidant N-acetylcysteine (NAC) or apocynin, an inhibitor of NADPH oxidase. Our data suggest that the HG-induced trophoblast spreading and the expression of PLAU, PAI-1, and MMP-9 were mediated by the production of ROS via NADPH oxidase activity. Our results shed light on placental alterations in gestational diabetes mellitus. © 2018 Wiley Periodicals, Inc.

Effect of Normobaric versus Hypobaric Oxygenation on Gaseous Microemboli Removal in a Diffusion Membrane Oxygenator: An In Vitro Comparison

PubMed Central

Schuldes, Matthew; Riley, Jeffrey B.; Francis, Stephen G.; Clingan, Sean

2016-01-01

Abstract: Gaseous microemboli (GME) are an abnormal physiological occurrence during cardiopulmonary bypass and extracorporeal membrane oxygenation (ECMO). Several studies have correlated negative sequelae with exposure to increased amounts of GME. Hypobaric oxygenation is effective at eliminating GME in hollow-fiber microporous membrane oxygenators. However, hollow-fiber diffusion membrane oxygenators, which are commonly used for ECMO, have yet to be validated. The purpose of this study was to determine if hypobaric oxygenation, compared against normobaric oxygenation, can reduce introduced GME when used on diffusion membrane oxygenators. Comparison of a sealed Quadrox-iD with hypobaric sweep gas (.67 atm) vs. an unmodified Quadrox-iD with normal atmospheric sweep gas (1 atm) in terms of GME transmission during continuous air introduction (50 mL/min) in a recirculating in vitro circuit, over a range of flow rates (3.5, 5 L/min) and crystalloid prime temperatures (37°C, 28°C, and 18°C). GME were measured using three EDAC Doppler probes positioned pre-oxygenator, post-oxygenator, and at the arterial cannula. Hypobaric oxygenation vs. normobaric oxygenation significantly reduced hollow-fiber diffusion membrane oxygenator GME transmission at all combination of pump flows and temperatures. There was further significant reduction in GME count between the oxygenator outlet and at the arterial cannula. Hypobaric oxygenation used on hollow-fiber diffusion membrane oxygenators can further reduce GME compared to normobaric oxygenation. This technique may be a safe approach to eliminate GME during ECMO. PMID:27729706

Mechanisms of lectin and antibody-dependent polymorphonuclear leukocyte-mediated cytolysis.

PubMed

Tsunawaki, S; Ikenami, M; Mizuno, D; Yamazaki, M

1983-04-01

The mechanisms of tumor lysis by polymorphonuclear leukocytes (PMNs) were investigated. In antibody-dependent PMN-mediated cytolysis (ADPC), sensitized tumor cells were specifically lysed via Fc receptors on PMNs. On the other hand, lectin-dependent PMN-mediated cytolysis (LDPC) caused nonspecific lysis of several murine tumors after recognition of carbohydrate moieties on the cell membrane of both PMNs and tumor cells. Both ADPC and LDPC depended on glycolysis, and cytotoxicity was mediated by reactive oxygen species; LDPC was dependent on superoxide and ADPC on the myeloperoxidase system. The participation of reactive oxygen species in PMN cytotoxicity was also demonstrated by pharmacological triggering with phorbol myristate acetate. These results indicate that reactive oxygen species have an important role In tumor killing by PMNs and that ADPC and LDPC have partly different cytolytic processes as well as different recognition steps.

MEDIATOR18 and MEDIATOR20 confer susceptibility to Fusarium oxysporum in Arabidopsis thaliana

PubMed Central

Stiller, Jiri; Davoine, Celine; Björklund, Stefan; Manners, John M.; Kazan, Kemal; Schenk, Peer M.

2017-01-01

The conserved protein complex known as Mediator conveys transcriptional signals by acting as an intermediary between transcription factors and RNA polymerase II. As a result, Mediator subunits play multiple roles in regulating developmental as well as abiotic and biotic stress pathways. In this report we identify the head domain subunits MEDIATOR18 and MEDIATOR20 as important susceptibility factors for Fusarium oxysporum infection in Arabidopsis thaliana. Mutants of MED18 and MED20 display down-regulation of genes associated with jasmonate signaling and biosynthesis while up-regulation of salicylic acid associated pathogenesis related genes and reactive oxygen producing and scavenging genes. We propose that MED18 and MED20 form a sub-domain within Mediator that controls the balance of salicylic acid and jasmonate associated defense pathways. PMID:28441405

Low Oxygen Tension Enhances Hepatitis C Virus Replication

PubMed Central

Kalliampakou, K. I.; Kotta-Loizou, I.; Befani, C.; Liakos, P.; Simos, G.; Mentis, A. F.; Kalliaropoulos, A.; Doumba, P. P.; Smirlis, D.; Foka, P.; Bauhofer, O.; Poenisch, M.; Windisch, M. P.; Lee, M. E.; Koskinas, J.; Bartenschlager, R.

2013-01-01

Low oxygen tension exerts a significant effect on the replication of several DNA and RNA viruses in cultured cells. In vitro propagation of hepatitis C virus (HCV) has thus far been studied under atmospheric oxygen levels despite the fact that the liver tissue microenvironment is hypoxic. In this study, we investigated the efficiency of HCV production in actively dividing or differentiating human hepatoma cells cultured under low or atmospheric oxygen tensions. By using both HCV replicons and infection-based assays, low oxygen was found to enhance HCV RNA replication whereas virus entry and RNA translation were not affected. Hypoxia signaling pathway-focused DNA microarray and real-time quantitative reverse transcription-PCR (qRT-PCR) analyses revealed an upregulation of genes related to hypoxic stress, glycolytic metabolism, cell growth, and proliferation when cells were kept under low (3% [vol/vol]) oxygen tension, likely reflecting cell adaptation to anaerobic conditions. Interestingly, hypoxia-mediated enhancement of HCV replication correlated directly with the increase in anaerobic glycolysis and creatine kinase B (CKB) activity that leads to elevated ATP production. Surprisingly, activation of hypoxia-inducible factor alpha (HIF-α) was not involved in the elevation of HCV replication. Instead, a number of oncogenes known to be associated with glycolysis were upregulated and evidence that these oncogenes contribute to hypoxia-mediated enhancement of HCV replication was obtained. Finally, in liver biopsy specimens of HCV-infected patients, the levels of hypoxia and anaerobic metabolism markers correlated with HCV RNA levels. These results provide new insights into the impact of oxygen tension on the intricate HCV-host cell interaction. PMID:23269812

High temperature mechanical properties of a zirconium-modified, precipitation- strengthened nickel, 30 percent copper alloy

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1974-01-01

A precipitation-strengthened Monel-type alloy has been developed through minor alloying additions of zirconium to a base Ni-30Cu alloy. The results of this exploratory study indicate that thermomechanical processing of a solution-treated Ni-30Cu-0.2Zr alloy produced a dispersion of precipitates. The precipitates have been tentatively identified as a Ni5Zr compound. A comparison of the mechanical properties, as determined by testing in air, of the zirconium-modified alloy to those of a Ni-30Cu alloy reveals that the precipitation-strengthened alloy has improved tensile properties to 1200 K and improved stress-rupture properties to 1100 K. The oxidation characteristics of the modified alloy appeared to be equivalent to those of the base Ni-30Cu alloy.

Effect of bottom water oxygenation on oxygen consumption and benthic biogeochemical processes at the Crimean Shelf (Black Sea)

NASA Astrophysics Data System (ADS)

Lichtschlag, A.; Janssen, F.; Wenzhöfer, F.; Holtappels, M.; Struck, U.; Jessen, G.; Boetius, A.

2012-04-01

Hypoxia occurs where oxygen concentrations fall below a physiological threshold of many animals, usually defined as <63 µmol L-1. Oxygen depletion can be caused by anthropogenic influences, such as global warming and eutrophication, but as well occurs naturally due to restricted water exchange in combination with high nutrient loads (e.g. upwelling). Bottom-water oxygen availability not only influences the composition of faunal communities, but is also one of the main factors controlling sediment-water exchange fluxes and organic carbon degradation in the sediment, usually shifting processes towards anaerobic mineralization pathways mediated by microorganisms. The Black Sea is one of the world's largest meromictic marine basins with an anoxic water column below 180m. The outer shelf edge, where anoxic waters meet the seafloor, is an ideal natural laboratory to study the response of benthic ecosystems to hypoxia, including benthic biogeochemical processes. During the MSM 15/1 expedition with the German research vessel MARIA S. MERIAN, the NW area of the Black Sea (Crimean Shelf) was studied. The study was set up to investigate the influence of bottom water oxygenation on, (1) the respective share of fauna-mediated oxygen uptake, microbial respiration, or re-oxidation of reduced compounds formed in the deeper sediments for the total oxygen flux and (2) on the efficiency of benthic biogeochemical cycles. During our study, oxygen consumption and pathways of organic carbon degradation were estimated from benthic chamber incubations, oxygen microprofiles measured in situ, and pore water and solid phase profiles measured on retrieved cores under oxic, hypoxic, and anoxic water column conditions. Benthic oxygen fluxes measured in Crimean Shelf sediments in this study were comparable to fluxes from previous in situ and laboratory measurements at similar oxygen concentrations (total fluxes -8 to -12 mmol m-2 d-1; diffusive fluxes: -2 to -5 mmol m-2 d-1) with oxygen

Intermittent hypoxia activates peptidylglycine α-amidating monooxygenase in rat brain stem via reactive oxygen species-mediated proteolytic processing

PubMed Central

Sharma, Suresh D.; Raghuraman, Gayatri; Lee, Myeong-Seon; Prabhakar, Nanduri R.; Kumar, Ganesh K.

2009-01-01

Intermittent hypoxia (IH) associated with sleep apneas leads to cardiorespiratory abnormalities that may involve altered neuropeptide signaling. The effects of IH on neuropeptide synthesis have not been investigated. Peptidylglycine α-amidating monooxygenase (PAM; EC 1.14.17.3) catalyzes the α-amidation of neuropeptides, which confers biological activity to a large number of neuropeptides. PAM consists of O2-sensitive peptidylglycine α-hydroxylating monooxygenase (PHM) and peptidyl-α-hydroxyglycine α-amidating lyase (PAL) activities. Here, we examined whether IH alters neuropeptide synthesis by affecting PAM activity and, if so, by what mechanisms. Experiments were performed on the brain stem of adult male rats exposed to IH (5% O2 for 15 s followed by 21% O2 for 5 min; 8 h/day for up to 10 days) or continuous hypoxia (0.4 atm for 10 days). Analysis of brain stem extracts showed that IH, but not continuous hypoxia, increased PHM, but not PAL, activity of PAM and that the increase of PHM activity was associated with a concomitant elevation in the levels of α-amidated forms of substance P and neuropeptide Y. IH increased the relative abundance of 42- and 35-kDa forms of PHM (∼1.6- and 2.7-fold, respectively), suggesting enhanced proteolytic processing of PHM, which appears to be mediated by an IH-induced increase of endoprotease activity. Kinetic analysis showed that IH increases Vmax but has no effect on Km. IH increased generation of reactive oxygen species in the brain stem, and systemic administration of antioxidant prevented IH-evoked increases of PHM activity, proteolytic processing of PHM, endoprotease activity, and elevations in substance P and neuropeptide Y amide levels. Taken together, these results demonstrate that IH activates PHM in rat brain stem via reactive oxygen species-dependent posttranslational proteolytic processing and further suggest that PAM activation may contribute to IH-mediated peptidergic neurotransmission in rat brain stem

Intermittent hypoxia activates peptidylglycine alpha-amidating monooxygenase in rat brain stem via reactive oxygen species-mediated proteolytic processing.

PubMed

Sharma, Suresh D; Raghuraman, Gayatri; Lee, Myeong-Seon; Prabhakar, Nanduri R; Kumar, Ganesh K

2009-01-01

Intermittent hypoxia (IH) associated with sleep apneas leads to cardiorespiratory abnormalities that may involve altered neuropeptide signaling. The effects of IH on neuropeptide synthesis have not been investigated. Peptidylglycine alpha-amidating monooxygenase (PAM; EC 1.14.17.3) catalyzes the alpha-amidation of neuropeptides, which confers biological activity to a large number of neuropeptides. PAM consists of O(2)-sensitive peptidylglycine alpha-hydroxylating monooxygenase (PHM) and peptidyl-alpha-hydroxyglycine alpha-amidating lyase (PAL) activities. Here, we examined whether IH alters neuropeptide synthesis by affecting PAM activity and, if so, by what mechanisms. Experiments were performed on the brain stem of adult male rats exposed to IH (5% O(2) for 15 s followed by 21% O(2) for 5 min; 8 h/day for up to 10 days) or continuous hypoxia (0.4 atm for 10 days). Analysis of brain stem extracts showed that IH, but not continuous hypoxia, increased PHM, but not PAL, activity of PAM and that the increase of PHM activity was associated with a concomitant elevation in the levels of alpha-amidated forms of substance P and neuropeptide Y. IH increased the relative abundance of 42- and 35-kDa forms of PHM ( approximately 1.6- and 2.7-fold, respectively), suggesting enhanced proteolytic processing of PHM, which appears to be mediated by an IH-induced increase of endoprotease activity. Kinetic analysis showed that IH increases V(max) but has no effect on K(m). IH increased generation of reactive oxygen species in the brain stem, and systemic administration of antioxidant prevented IH-evoked increases of PHM activity, proteolytic processing of PHM, endoprotease activity, and elevations in substance P and neuropeptide Y amide levels. Taken together, these results demonstrate that IH activates PHM in rat brain stem via reactive oxygen species-dependent posttranslational proteolytic processing and further suggest that PAM activation may contribute to IH-mediated peptidergic

Physiology of Oxygen Breathing in Pilots: A Brief Review

DTIC Science & Technology

2018-03-23

brief review Abstract This non-exhaustive survey presents literature describing some effects of breathing oxygen partial pressures between...CG, J Butler, AB DuBois (1959). Some effects of restriction of chest cage expansion on pulmonary function in man: an experimental study. J Clin...Effects of Submerged Breathing of Air or Oxygen. Navy Experimental Diving Unit TR 02-14, Panama City, FL. http://archive.rubicon- foundation.org/3483

Reaction of Titanium and Zirconium Particles in Cylindrical Explosive Charges

NASA Astrophysics Data System (ADS)

Frost, David; Cairns, Malcolm; Goroshin, Samuel; Zhang, Fan

2007-06-01

The critical conditions for the reaction of high melting-point metallic particles (Ti, Zr) dispersed during the detonation of long cylindrical explosive charges have been investigated experimentally. The charges consisted of packed beds of either spherical titanium particles (with diameters of 35, 90, or 215 μm; AP&C, Inc.) or nonspherical zirconium particles (250 -- 500 μm or 500 -- 600 μm, Atlantic Equipment Eng., NJ) saturated with sensitized liquid nitromethane. For the titanium particles, a threshold particle diameter exists, above which self-sustained particle reaction is not observed, although some particle reaction occurs immediately behind the detonation front then rapidly quenches. For the smallest particles, the proportion of the conical particle cloud that reacts increases with charge diameter, suggesting that the reaction initiation is a competition between particle heating and expansion cooling of the products. For zirconium particles, no critical conditions exist; particle ignition was observed for all particle and charge diameters tested. In this case, interaction of the high pressure detonation wave with the particles is sufficient to initiate reaction at the particle surface after a delay time (˜ 10's μs), which is much less than the time required for thermal equilibration of the particles.

η(6) -Arene-Zirconium-PNP-Pincer Complexes: Mechanism of Their Hydrogenolytic Formation and Their Reactivity as Zirconium(II) Synthons.

PubMed

Plundrich, Gudrun T; Wadepohl, Hubert; Clot, Eric; Gade, Lutz H

2016-06-27

The cyclometalated monobenzyl complexes [(Cbzdiphos(R) -CH)ZrBnX] 1 (iPr) Cl and 1 (Ph) I reacted with dihydrogen (10 bar) to yield the η(6) -toluene complexes [(Cbzdiphos(R) )Zr(η(6) -tol)X] 2 (iPr) Cl and 2 (Ph) I (cbzdiphos=1,8-bis(phosphino)-3,6-di-tert-butyl-9H-carbazole). The arene complexes were also found to be directly accessible from the triiodide [(Cbzdiphos(Ph) )ZrI3 ] through an in situ reaction with a dibenzylmagnesium reagent and subsequent hydrogenolysis, as exemplified for the η(6) -mesitylene complex [(Cbzdiphos(Ph) )Zr(η(6) -mes)I] (3 (Ph) I). The tolyl-ring in 2 (iPr) Cl adopts a puckered arrangement (fold angle 23.3°) indicating significant arene-1,4-diido character. Deuterium labeling experiments were consistent with an intramolecular reaction sequence after the initial hydrogenolysis of a Zr-C bond by a σ-bond metathesis. A DFT study of the reaction sequence indicates that hydrogenolysis by σ-bond metathesis first occurs at the cyclometalated ancillary ligand giving a hydrido-benzyl intermediate, which subsequently reductively eliminates toluene that then coordinates to the Zr atom as the reduced arene ligand. Complex 2 (Ph) I was reacted with 2,6-diisopropylphenyl isocyanide giving the deep blue, diamagnetic Zr(II) -diisocyanide complex [(Cbzdiphos(Ph) )Zr(CNDipp)2 I] (4 (Ph) I). DFT modeling of 4 (Ph) I demonstrated that the HOMO of the complex is primarily located as a "lone pair on zirconium", with some degree of back-bonding into the C≡N π* bond, and the complex is thus most appropriately described as a zirconium(II) species. Reaction of 2 (Ph) I with trimethylsilylazide (N3 TMS) and 2 (iPr) Cl with 1-azidoadamantane (N3 Ad) resulted in the formation of the imido complexes [(Cbzdiphos(R) )Zr=NR'(X)] 5 (iPr) Cl-NAd and 5 (Ph) I-NTMS, respectively. Reaction of 2 (iPr) Cl with azobenzene led to N-N bond scission giving 6 (iPr) Cl, in which one of the NPh-fragments is coupled with the carbazole

A single active site residue directs oxygenation stereospecificity in lipoxygenases: Stereocontrol is linked to the position of oxygenation

PubMed Central

Coffa, Gianguido; Brash, Alan R.

2004-01-01

Lipoxygenases are a class of dioxygenases that form hydroperoxy fatty acids with distinct positional and stereo configurations. Several amino acid residues influencing regiospecificity have been identified, whereas the basis of stereocontrol is not understood. We have now identified a single residue in the lipoxygenase catalytic domain that is important for stereocontrol; it is conserved as an Ala in S lipoxygenases and a Gly in R lipoxygenases. Our results with mutation of the conserved Ala to Gly in two S lipoxygenases (mouse 8S-LOX and human 15-LOX-2) and the corresponding Gly–Ala substitution in two R lipoxygenases (human 12R-LOX and coral 8R-LOX) reveal that the basis for R or S stereo-control also involves a switch in the position of oxygenation on the substrate. After the initial hydrogen abstraction, antarafacial oxygenation at one end or the other of the activated pair of double bonds (pentadiene) gives, for example, 8S or 12R product. The Ala residue promotes oxygenation on the reactive pentadiene at the end deep in the substrate binding pocket and S stereochemistry of the product hydroperoxide, and a Gly residue promotes oxygenation at the proximal end of the reactive pentadiene resulting in R stereochemistry. A model of lipoxygenase reaction specificity is proposed in which product regiochemistry and stereochemistry are determined by fixed relationships between substrate orientation, hydrogen abstraction, and the Gly or Ala residue we have identified. PMID:15496467

Reactive oxygen species mediates homocysteine-induced mitochondrial biogenesis in human endothelial cells: Modulation by antioxidants

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

Perez-de-Arce, Karen; Departamento de Biologia Celular y Molecular, Facultad de Ciencias Biologicas, Pontificia Universidad Catolica de Chile, Santiago; Foncea, Rocio

2005-12-16

It has been proposed that homocysteine (Hcy)-induces endothelial dysfunction and atherosclerosis by generation of reactive oxygen species (ROS). A previous report has shown that Hcy promotes mitochondrial damage. Considering that oxidative stress can affect mitochondrial biogenesis, we hypothesized that Hcy-induced ROS in endothelial cells may lead to increased mitochondrial biogenesis. We found that Hcy-induced ROS (1.85-fold), leading to a NF-{kappa}B activation and increase the formation of 3-nitrotyrosine. Furthermore, expression of the mitochondrial biogenesis factors, nuclear respiratory factor-1 and mitochondrial transcription factor A, was significantly elevated in Hcy-treated cells. These changes were accompanied by increase in mitochondrial mass and higher mRNAmore » and protein expression of the subunit III of cytochrome c oxidase. These effects were significantly prevented by pretreatment with the antioxidants, catechin and trolox. Taken together, our results suggest that ROS is an important mediator of mitochondrial biogenesis induced by Hcy, and that modulation of oxidative stress by antioxidants may protect against the adverse vascular effects of Hcy.« less

Signal Transducers and Activators of Transcription: STATs-Mediated Mitochondrial Neuroprotection

PubMed Central

Lin, Hung Wen; Thompson, John W.; Morris, Kahlilia C.

2011-01-01

Abstract Cerebral ischemia is defined as little or no blood flow in cerebral circulation, characterized by low tissue oxygen and glucose levels, which promotes neuronal mitochondria dysfunction leading to cell death. A strategy to counteract cerebral ischemia-induced neuronal cell death is ischemic preconditioning (IPC). IPC results in neuroprotection, which is conferred by a mild ischemic challenge prior to a normally lethal ischemic insult. Although many IPC-induced mechanisms have been described, many cellular and subcellular mechanisms remain undefined. Some reports have suggested key signal transduction pathways of IPC, such as activation of protein kinase C epsilon, mitogen-activated protein kinase, and hypoxia-inducible factors, that are likely involved in IPC-induced mitochondria mediated-neuroprotection. Moreover, recent findings suggest that signal transducers and activators of transcription (STATs), a family of transcription factors involved in many cellular activities, may be intimately involved in IPC-induced ischemic tolerance. In this review, we explore current signal transduction pathways involved in IPC-induced mitochondria mediated-neuroprotection, STAT activation in the mitochondria as it relates to IPC, and functional significance of STATs in cerebral ischemia. Antioxid. Redox Signal. 14, 1853–1861. PMID:20712401

Pyroelectric response in crystalline hafnium zirconium oxide (Hf 1- x Zr x O 2 ) thin films

DOE PAGES

Smith, S. W.; Kitahara, A. R.; Rodriguez, M. A.; ...

2017-02-13

Pyroelectric coefficients were measured for 20 nm thick crystalline hafnium zirconium oxide (Hf 1-xZr xO 2) thin films across a composition range of 0 ≤ x ≤ 1. Pyroelectric currents were collected near room temperature under zero applied bias and a sinusoidal oscillating temperature profile to separate the influence of non-pyroelectric currents. The pyroelectric coefficient was observed to correlate with zirconium content, increased orthorhombic/tetragonal phase content, and maximum polarization response. The largest measured absolute value was 48 μCm -2K -1 for a composition with x = 0.64, while no pyroelectric response was measured for compositions which displayed no remanent polarizationmore » (x = 0, 0.91, 1).« less

Reconstruing intolerance: abstract thinking reduces conservatives' prejudice against nonnormative groups.

PubMed

Luguri, Jamie B; Napier, Jaime L; Dovidio, John F

2012-07-01

Myrdal (1944) described the "American dilemma" as the conflict between abstract national values ("liberty and justice for all") and more concrete, everyday prejudices. We leveraged construal-level theory to empirically test Myrdal's proposition that construal level (abstract vs. concrete) can influence prejudice. We measured individual differences in construal level (Study 1) and manipulated construal level (Studies 2 and 3); across these three studies, we found that adopting an abstract mind-set heightened conservatives' tolerance for groups that are perceived as deviating from Judeo-Christian values (gay men, lesbians, Muslims, and atheists). Among participants who adopted a concrete mind-set, conservatives were less tolerant of these nonnormative groups than liberals were, but political orientation did not have a reliable effect on tolerance among participants who adopted an abstract mind-set. Attitudes toward racial out-groups and dominant groups (e.g., Whites, Christians) were unaffected by construal level. In Study 3, we found that the effect of abstract thinking on prejudice was mediated by an increase in concerns about fairness.

Distribution coefficients of rare earth ions in cubic zirconium dioxide

NASA Astrophysics Data System (ADS)

Romer, H.; Luther, K.-D.; Assmus, W.

1994-08-01

Cubic zirconium dioxide crystals are grown with the skull melting technique. The effective distribution coefficients for Nd(exp 3+), Sm(exp 3+) and Er(sup 3+) as dopants are determined experimentally as a function of the crystal growth velocity. With the Burton-Prim-Slichter theory, the equilibrium distribution coefficients can be calculated. The distribution coefficients of all other trivalent rare earth ions can be estimated by applying the correlation towards the ionic radii.

Oxidized zirconium versus cobalt-chromium against the native patella in total knee arthroplasty: Patellofemoral outcomes.

PubMed

Matassi, Fabrizio; Paoli, Tommaso; Civinini, Roberto; Carulli, Christian; Innocenti, Massimo

2017-10-01

Oxidized zirconium (OxZr) has demonstrated excellent mechanical properties in vitro when used against articular cartilage; less coefficient of friction and less chondral damage have been found when compared with cobalt-chromium (CoCr) implants. However, controversy exists as to whether implants with a zirconium femoral component articulate safely with a native patella in total knee arthroplasty (TKA). To answer this question, the clinical and radiographic results were analysed from a group of patients who underwent a TKA with patella retention; the OxZr versus CoCr femoral components were compared. The present study prospectively evaluated 83 knees of 74 patients from 2009 to 2010. Each patient was evaluated clinically (visual analogue scale, Knee Society score, patellar score) and radiographically (long leg standing radiograph, anterior-posterior and latero-lateral projections, axial view of the patella) pre-operatively and postoperatively with a mean follow-up of 4.47years. The patellar tilt and shift, and progression of patellofemoral osteoarthritis were calculated with the axial view. There were no patient reported adverse reactions and none of the evaluated prostheses failed. Both the clinical and radiographic evaluations showed no statistically significant between-group differences. No adverse events were observed clinically or radiologically. These results justify pursuing the use of oxidized zirconium as an alternative bearing surface for a femoral component associated with patellar retention in TKA. Published by Elsevier B.V.

Influence of chemical composition of zirconium alloy E110 on embrittlement under LOCA conditions - Part 1: Oxidation kinetics and macrocharacteristics of structure and fracture

NASA Astrophysics Data System (ADS)

Nikulin, S. A.; Rozhnov, A. B.; Belov, V. A.; Li, E. V.; Glazkina, V. S.

2011-11-01

Exploratory investigations of the influence of alloying and impurity content in the E110 alloy cladding tubes on the behavior under conditions of Loss of Coolant Accidents (LOCA) has been performed. Three alloys of E110 type have been tested: E110 alloy of nominal composition Zr-1%Nb (E110), E110 alloy of modified composition Zr-1%Nb-0.12%Fe-0.13%O (E110M), E110 alloy of nominal composition Zr-1%Nb with reduced impurity content (E110G). Alloys E110 and E110M were manufactured on the electrolytic basis and alloy E110G was manufactured on the basis of zirconium sponge. The high temperature oxidation tests in steam ( T = 1100 °C, 18% of equivalent cladding reacted (ECR)) have been conducted, kinetics of oxidation was investigated. Quantitative research of structure and fracture macrocharacteristics was performed by means of optical and electron microscopy. The results received were compared with the residual ductility of specimens. The results of the investigation showed the existence of "breakaway oxidation" kinetics and white spalling oxide in E110 and E110M alloys while the specimen oxidation kinetics in E110G alloy was characterized by a parabolic law and specimens had a dense black oxide. Oxygen and iron alloying in the E110 alloy positively changed the macrocharacteristics of structure and fracture. However, in general, it did not improve the resistance to embrittlement in LOCA conditions apparently because of a strong impurity influence caused by electrolytic process of zirconium production.

Retention of implant-supported zirconium oxide ceramic restorations using different luting agents.

PubMed

Nejatidanesh, Farahnaz; Savabi, Omid; Shahtoosi, Mojtaba

2013-08-01

The aim of this study was to evaluate the retention value of implant-supported zirconium oxide ceramic copings using different luting agents. Twenty ITI solid abutments of 5.5 mm height and ITI implant analogs were mounted vertically into autopolymerizing acrylic resin blocks. Ninety zirconium oxide copings (Cercon, Degudent) with a loop on the occlusal portion were made. All samples were airborne particle abraded with 110 μm Al₂O₃ and luted using different types of luting agents: resin cements (Clearfil SA, Panavia F2.0, Fuji Plus), conventional cements (Fleck's, Poly F, Fuji I), and temporary cements (Temp Bond, GC free eugenol, TempSpan) with a load of 5 Kg. (N = 10) All copings were incubated at 37°C for 24 h and conditioned in artificial saliva for 1 week, and thermal cycled for 5000 cycles 5-55°C with a 30-s dwell time. The dislodging force of the copings along the long axis of the implant-abutment complex was recorded using universal testing machine with 5 mm/min crosshead speed. Data were subjected to Kruskal-Wallis (α = 0.05) and Mann-Whitney tests with Bonferroni step down correction (α = 0.001). There was significant difference between the mean rank retention values of different luting agents (P < 0.001). The resin cements showed the highest retention (Clearfil SA, 203.49 ± 52.86; Fuji Plus, 190.61 ± 48.00; Panavia F 2.0, 172.16 ± 70.76 N). The conventional cements had more retention than the temporary cements and glass ionomer cement (P < 0.001). The retention of zircona ceramic restorations, over ITI solid abutments may be influenced by the type of cement. The application of an MDP-containing resin and resin-modified glass ionomer luting agents increase the retentive value of implant-supported zirconium oxide restorations. © 2011 John Wiley & Sons A/S.

Oxygen-Inducible Glutamate Oxaloacetate Transaminase as Protective Switch Transforming Neurotoxic Glutamate to Metabolic Fuel During Acute Ischemic Stroke

PubMed Central

Rink, Cameron; Gnyawali, Surya; Peterson, Laura

2011-01-01

Abstract This work rests on our previous report (J Cereb Blood Flow Metab 30: 1275–1287, 2010) recognizing that glutamate (Glu) oxaloacetate transaminase (GOT) is induced when brain tissue hypoxia is corrected during acute ischemic stroke (AIS). GOT can metabolize Glu into tricarboxylic acid cycle intermediates and may therefore be useful to harness excess neurotoxic extracellular Glu during AIS as a metabolic substrate. We report that in cultured neural cells challenged with hypoglycemia, extracellular Glu can support cell survival as long as there is sufficient oxygenation. This effect is abrogated by GOT knockdown. In a rodent model of AIS, supplemental oxygen (100% O2 inhaled) during ischemia significantly increased GOT expression and activity in the stroke-affected brain tissue and prevented loss of ATP. Biochemical analyses and in vivo magnetic resonance spectroscopy during stroke demonstrated that such elevated GOT decreased Glu levels at the stroke-affected site. In vivo lentiviral gene delivery of GOT minimized lesion volume, whereas GOT knockdown worsened stroke outcomes. Thus, brain tissue GOT emerges as a novel target in managing stroke outcomes. This work demonstrates that correction of hypoxia during AIS can help clear extracellular neurotoxic Glu by enabling utilization of this amino acid as a metabolic fuel to support survival of the hypoglycemic brain tissue. Strategies to mitigate extracellular Glu-mediated neurodegeneration via blocking receptor-mediated excitotoxicity have failed in clinical trials. We introduce the concept that under hypoglycemic conditions extracellular Glu can be transformed from a neurotoxin to a survival factor by GOT, provided there is sufficient oxygen to sustain cellular respiration. Antioxid. Redox Signal. 14, 1777–1785. PMID:21361730

Singlet Oxygen Generation Mediated By Silicon Nanocrystal Assemblies

DTIC Science & Technology

2011-01-01

Lattice fringes in Fig.3 d correspond to the (111) atomic planes of Si nanocrystals. Length scales are indicated. Downscaling of the stain etched PSi...intensity of 1W/cm2 in a time scale of a few hours a monolayer of oxygen is formed on the surface of Si nanocrystals. Fig. 8. Infrared absorption...solution. Fig. 10. PL intensity as a function of continuously prolonged etching of Si powder. Inset: PL suppression level (can be scaled as singlet

Nanocrystalline diamond protects Zr cladding surface against oxygen and hydrogen uptake: Nuclear fuel durability enhancement.

PubMed

Škarohlíd, Jan; Ashcheulov, Petr; Škoda, Radek; Taylor, Andrew; Čtvrtlík, Radim; Tomáštík, Jan; Fendrych, František; Kopeček, Jaromír; Cháb, Vladimír; Cichoň, Stanislav; Sajdl, Petr; Macák, Jan; Xu, Peng; Partezana, Jonna M; Lorinčík, Jan; Prehradná, Jana; Steinbrück, Martin; Kratochvílová, Irena

2017-07-25

In this work, we demonstrate and describe an effective method of protecting zirconium fuel cladding against oxygen and hydrogen uptake at both accident and working temperatures in water-cooled nuclear reactor environments. Zr alloy samples were coated with nanocrystalline diamond (NCD) layers of different thicknesses, grown in a microwave plasma chemical vapor deposition apparatus. In addition to showing that such an NCD layer prevents the Zr alloy from directly interacting with water, we show that carbon released from the NCD film enters the underlying Zr material and changes its properties, such that uptake of oxygen and hydrogen is significantly decreased. After 100-170 days of exposure to hot water at 360 °C, the oxidation of the NCD-coated Zr plates was typically decreased by 40%. Protective NCD layers may prolong the lifetime of nuclear cladding and consequently enhance nuclear fuel burnup. NCD may also serve as a passive element for nuclear safety. NCD-coated ZIRLO claddings have been selected as a candidate for Accident Tolerant Fuel in commercially operated reactors in 2020.

Irradiation-induced effects of proton irradiation on zirconium carbides with different stoichiometries

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

Y. Huang; B.R. Maier; T.R. Allen

2014-10-01

Zirconium carbide (ZrC) is being considered for utilization in deep burn TRISO fuel particles for hightemperature, gas-cooled reactors. Zirconium carbide has a cubic B1 type crystal structure along with a very high melting point (3420 ?C), exceptional hardness and good thermal and electrical conductivities. Understanding the ZrC irradiation response is crucial for establishing ZrC as an alternative component in TRISO fuel. Until now, very few studies on irradiation effects on ZrC have been released and fundamental aspects of defect evolution and kinetics are not well understood although some atomistic simulations and phenomenological studies have been performed. This work was carriedmore » out to understand the damage evolution in float-zone refined ZrC with different stoichiometries. Proton irradiations at 800 ?C up to doses of 3 dpa were performed on ZrCx (where x ranges from 0.9 to 1.2) to investigate the damage evolution. The irradiation-induced defects, such as density of dislocation loops, at different stoichiometries and doses which were characterized by transmission electron microscopy (TEM) is presented and discussed.« less

Improved Yttrium and Zirconium Abundances in Metal-Poor Stars

NASA Astrophysics Data System (ADS)

Violante, Renata; Biemont, E.; Cowan, J. J.; Sneden, C.

2012-01-01

Abstract We present new abundances of the lighter n-capture elements, Yttrium (Z=39) and Zirconium (Z=40) in the very metal poor, r-process rich stars BD+17 3248 and HD 221170. Very accurate abundances were obtained by use of the new transition probabilities for Y II published by Biémont et al. 2011, and Zr II by Malcheva et al. 2006, and by expanding the number of transitions employed for each element. For example, in BD+17 3248, we find log ɛπσιλον=-0.03 +/- 0.03 (σιγμα=0.15, from 23 lines) for Y II. As for Zr II, log ɛπσιλον = 0.65 +/- 0.03 (σɛγμα = 0.1, from 13 lines). The resulting abundance ratio is log ɛπσιλον [Y/Zr] = -0.68 +/- 0.05. The results for HD 221170 are in accord with those of BD+17 3248. The quantity of lines used to form the abundance means has increased significantly since the original studies of these stars, resulting in more trustworthy abundances. These observed abundance ratios are in agreement with an r-process-only value predicted from stellar models, but is under-abundant compared to an empirical model derived from direct analyses of meteoritic material. This ambiguity should stimulate further nucleosynthetic analysis to explain this abundance ratio. We would like to extend our gratitude to NSF grant AST-0908978 and the University of Texas Astronomy Department Rex G. Baker, Jr. Endowment for their financial support in this project.

Isotopic Composition of Oxygen in Lunar Zircons

NASA Technical Reports Server (NTRS)

Nemchin, A. A.; Whitehouse, M. J.; Pidgeon, R. T.; Meyer, C.

2005-01-01

The recent discovery of heavy oxygen in zircons from the Jack Hills conglomerates Wilde et al. and Mojzsis et al. was interpreted as an indication of presence of liquid water on the surface of Early Earth. The distribution of ages of Jack Hills zircons and lunar zircons appears to be very similar and therefore analysis of oxygen in the lunar grains may provide a reference frame for further study of the early history of the Earth as well as give additional information regarding processes that operated on the Moon. In the present study we have analysed the oxygen isotopic composition of zircon grains from three lunar samples using the Swedish Museum of Natural History CAMECA 1270 ion microprobe. The samples were selected as likely tests for variations in lunar oxygen isotopic composition. Additional information is included in the original extended abstract.

HIF Oxygen Sensing Pathways in Lung Biology.

PubMed

Urrutia, Andrés A; Aragonés, Julián

2018-06-06

Cellular responses to oxygen fluctuations are largely mediated by hypoxia-inducible factors (HIFs). Upon inhalation, the first organ inspired oxygen comes into contact with is the lungs, but the understanding of the pulmonary HIF oxygen-sensing pathway is still limited. In this review we will focus on the role of HIF1α and HIF2α isoforms in lung responses to oxygen insufficiency. In particular, we will discuss novel findings regarding their role in the biology of smooth muscle cells and endothelial cells in the context of hypoxia-induced pulmonary vasoconstriction. Moreover, we will also discuss recent studies into HIF-dependent responses in the airway epithelium, which have been even less studied than the HIF-dependent vascular responses in the lungs. In summary, we will review the biological functions executed by HIF1 or HIF2 in the pulmonary vessels and epithelium to control lung responses to oxygen fluctuations as well as their pathological consequences in the hypoxic lung.

Beyond the classic eicosanoids: Peripherally-acting oxygenated metabolites of polyunsaturated fatty acids mediate pain associated with tissue injury and inflammation.

PubMed

Shapiro, Haim; Singer, Pierre; Ariel, Amiram

2016-08-01

Pain is a complex sensation that may be protective or cause undue suffering and loss of function, depending on the circumstances. Peripheral nociceptor neurons (PNs) innervate most tissues, and express ion channels, nocisensors, which depolarize the cell in response to intense stimuli and numerous substances. Inflamed tissues manifest inflammatory hyperalgesia in which the threshold for pain and the response to painful stimuli are decreased and increased, respectively. Constituents of the inflammatory milieu sensitize PNs, thereby contributing to hyperalgesia. Polyunsaturated fatty acids undergo enzymatic and free radical-mediated oxygenation into an array of bioactive metabolites, oxygenated polyunsaturated fatty acids (oxy-PUFAs), including the classic eicosanoids. Oxy-PUFA production is enhanced during inflammation. Pioneering studies by Vane and colleagues from the early 1970s first implicated classic eicosanoids in the pain associated with inflammation. Here, we review the production and action of oxy-PUFAs that are not classic eicosanoids, but nevertheless are produced in injured/ inflamed tissues and activate or sensitize PNs. In general, oxy-PUFAs that sensitize PNs may do so directly, by activation of nocisensors, ion channels or GPCRs expressed on the surface of PNs, or indirectly, by increasing the production of inflammatory mediators that activate or sensitize PNs. We focus on oxy-PUFAs that act directly on PNs. Specifically, we discuss the role of arachidonic acid-derived 12S-HpETE, HNE, ONE, PGA2, iso-PGA2 and 15d-PGJ2, 5,6-and 8,9-EET, PGE2-G and 8R,15S-diHETE, as well as the linoleic acid-derived 9-and 13-HODE in inducing acute nocifensive behavior and/or inflammatory hyperalgesia in rodents. The nocisensors TRPV1, TRPV4 and TRPA1, and putative Gαs-type GPCRs are the PN targets of these oxy-PUFAs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Silibinin activates AMP-activated protein kinase to protect neuronal cells from oxygen and glucose deprivation-re-oxygenation.

PubMed

Xie, Zhi; Ding, Sheng-quan; Shen, Ya-fang

2014-11-14

In this study, we explored the cytoprotective potential of silibinin against oxygen-glucose deprivation (OGD)-induced neuronal cell damages, and studied underling mechanisms. In vitro model of ischemic stroke was created by keeping neuronal cells (SH-SY5Y cells and primary mouse cortical neurons) in an OGD condition followed by re-oxygenation. Pre-treatment of silibinin significantly inhibited OGD/re-oxygenation-induced necrosis and apoptosis of neuronal cells. OGD/re-oxygenation-induced reactive oxygen species (ROS) production and mitochondrial membrane potential (MMP) reduction were also inhibited by silibinin. At the molecular level, silibinin treatment in SH-SY5Y cells and primary cortical neurons led to significant AMP-activated protein kinase (AMPK) signaling activation, detected by phosphorylations of AMPKα1, its upstream kinase liver kinase B1 (LKB1) and the downstream target acetyl-CoA Carboxylase (ACC). Pharmacological inhibition or genetic depletion of AMPK alleviated the neuroprotective ability of silibinin against OGD/re-oxygenation. Further, ROS scavenging ability by silibinin was abolished with AMPK inhibition or silencing. While A-769662, the AMPK activator, mimicked silibinin actions and suppressed ROS production and neuronal cell death following OGD/re-oxygenation. Together, these results show that silibinin-mediated neuroprotection requires activation of AMPK signaling. Copyright © 2014 Elsevier Inc. All rights reserved.

White Paper Summary of 2nd ASTM International Workshop on Hydrides in Zirconium Alloy Cladding

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

Sindelar, R.; Louthan, M.; PNNL, B.

2015-05-29

This white paper recommends that ASTM International develop standards to address the potential impact of hydrides on the long term performance of irradiated zirconium alloys. The need for such standards was apparent during the 2nd ASTM International Workshop on Hydrides in Zirconium Alloy Cladding and Assembly Components, sponsored by ASTM International Committee C26.13 and held on June 10-12, 2014, in Jackson, Wyoming. The potentially adverse impacts of hydrogen and hydrides on the long term performance of irradiated zirconium-alloy cladding on used fuel were shown to depend on multiple factors such as alloy chemistry and processing, irradiation and post irradiation history,more » residual and applied stresses and stress states, and the service environment. These factors determine the hydrogen content and hydride morphology in the alloy, which, in turn, influence the response of the alloy to the thermo-mechanical conditions imposed (and anticipated) during storage, transport and disposal of used nuclear fuel. Workshop presentations and discussions showed that although hydrogen/hydride induced degradation of zirconium alloys may be of concern, the potential for occurrence and the extent of anticipated degradation vary throughout the nuclear industry because of the variations in hydrogen content, hydride morphology, alloy chemistry and irradiation conditions. The tools and techniques used to characterize hydrides and hydride morphologies and their impacts on material performance also vary. Such variations make site-to-site comparisons of test results and observations difficult. There is no consensus that a single material or system characteristic (e.g., reactor type, burnup, hydrogen content, end-of life stress, alloy type, drying temperature, etc.) is an effective predictor of material response during long term storage or of performance after long term storage. Multi-variable correlations made for one alloy may not represent the behavior of another alloy exposed

Somatic Pairing of Chromosome 19 in Renal Oncocytoma Is Associated with Deregulated ELGN2-Mediated Oxygen-Sensing Response

PubMed Central

Petillo, David; Westphal, Michael; Koelzer, Katherine; Metcalf, Julie L.; Zhang, Zhongfa; Matsuda, Daisuke; Dykema, Karl J.; Houseman, Heather L.; Kort, Eric J.; Furge, Laura L.; Kahnoski, Richard J.; Richard, Stéphane; Vieillefond, Annick; Swiatek, Pamela J.; Teh, Bin Tean; Ohh, Michael; Furge, Kyle A.

2008-01-01

Chromosomal abnormalities, such as structural and numerical abnormalities, are a common occurrence in cancer. The close association of homologous chromosomes during interphase, a phenomenon termed somatic chromosome pairing, has been observed in cancerous cells, but the functional consequences of somatic pairing have not been established. Gene expression profiling studies revealed that somatic pairing of chromosome 19 is a recurrent chromosomal abnormality in renal oncocytoma, a neoplasia of the adult kidney. Somatic pairing was associated with significant disruption of gene expression within the paired regions and resulted in the deregulation of the prolyl-hydroxylase ELGN2, a key protein that regulates the oxygen-dependent degradation of hypoxia-inducible factor (HIF). Overexpression of ELGN2 in renal oncocytoma increased ubiquitin-mediated destruction of HIF and concomitantly suppressed the expression of several HIF-target genes, including the pro-death BNIP3L gene. The transcriptional changes that are associated with somatic pairing of chromosome 19 mimic the transcriptional changes that occur following DNA amplification. Therefore, in addition to numerical and structural chromosomal abnormalities, alterations in chromosomal spatial dynamics should be considered as genomic events that are associated with tumorigenesis. The identification of EGLN2 as a significantly deregulated gene that maps within the paired chromosome region directly implicates defects in the oxygen-sensing network to the biology of renal oncocytoma. PMID:18773095

A mutation in the mitochondrial protein UQCRB promotes angiogenesis through the generation of mitochondrial reactive oxygen species

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

Chang, Junghwa; Jung, Hye Jin; Jeong, Seung Hun

2014-12-12

Highlights: • We constructed mitochondrial protein UQCRB mutant stable cell lines on the basis of a human case report. • These mutant cell lines exhibit pro-angiogenic activity with enhanced VEGF expression. • Proliferation of mutant cell lines was regulated by UQCRB inhibitors. • UQCRB may have a functional role in angiogenesis. - Abstract: Ubiquinol-cytochrome c reductase binding protein (UQCRB) is one of the subunits of mitochondrial complex III and is a target protein of the natural anti-angiogenic small molecule terpestacin. Previously, the biological role of UQCRB was thought to be limited to the maintenance of complex III. However, the identificationmore » and validation of UQCRB as a target protein of terpestacin enabled the role of UQCRB in oxygen sensing and angiogenesis to be elucidated. To explore the biological role of this protein further, UQCRB mutant stable cell lines were generated on the basis of a human case report. We demonstrated that these cell lines exhibited glycolytic and pro-angiogenic activities via mitochondrial reactive oxygen species (mROS)-mediated HIF1 signal transduction. Furthermore, a morphological abnormality in mitochondria was detected in UQCRB mutant stable cell lines. In addition, the proliferative effect of the UQCRB mutants was significantly regulated by the UQCRB inhibitors terpestacin and A1938. Collectively, these results provide a molecular basis for UQCRB-related biological processes and reveal potential key roles of UQCRB in angiogenesis and mitochondria-mediated metabolic disorders.« less

Role of reactive oxygen intermediates in the interferon-mediated depression of hepatic drug metabolism and protective effect of N-acetylcysteine in mice.

PubMed

Ghezzi, P; Bianchi, M; Gianera, L; Landolfo, S; Salmona, M

1985-08-01

Interferon (IFN) and IFN inducers are known to depress hepatic microsomal cytochrome P-450 levels, and the liver toxicity of IFN was reported to be lethal in newborn mice. We have observed that administration to mice of IFN and IFN inducers caused a marked increase in liver xanthine oxidase activity. Because this enzyme is well known to produce reactive oxygen intermediates and cytochrome P-450 was reported to be sensitive to the oxidative damage, we have tested the hypothesis that a free radical mechanism could mediate the depression of cytochrome P-450 levels by IFN. Administration to mice of the IFN inducer polyinosinic-polycytidylic acid (2 mg/kg i.p.) caused a 29 to 52% decrease in liver cytochrome P-450. Concomitant p.o. administration of the free radical scavenger, N-acetylcysteine (as a 2.5% solution in drinking water), or the xanthine oxidase inhibitor, allopurinol (100 mg/kg), protected against the IFN-mediated depression of P-450 kg), protected against the IFN-mediated depression of P-450 levels. The results suggest that an increased endogenous generation of free radicals, possibly due to the induction of xanthine oxidase, is implicated in the IFN-mediated depression of liver drug metabolism. The relevance of these data also extends to cases in which this side effect is observed in pathological situations (e.g., viral diseases and administration of vaccines) associated with an induction of IFN.

A PP2A-mediated feedback mechanism controls Ca2+-dependent NO synthesis under physiological oxygen.

PubMed

Keeley, Thomas P; Siow, Richard C M; Jacob, Ron; Mann, Giovanni E

2017-12-01

Intracellular O 2 is a key regulator of NO signaling, yet most in vitro studies are conducted in atmospheric O 2 levels, hyperoxic with respect to the physiologic milieu. We investigated NO signaling in endothelial cells cultured in physiologic (5%) O 2 and stimulated with histamine or shear stress. Culture of cells in 5% O 2 (>5 d) decreased histamine- but not shear stress-stimulated endothelial (e)NOS activity. Unlike cells adapted to a hypoxic environment (1% O 2 ), those cultured in 5% O 2 still mobilized sufficient Ca 2+ to activate AMPK. Enhanced expression and membrane targeting of PP2A-C was observed in 5% O 2 , resulting in greater interaction with eNOS in response to histamine. Moreover, increased dephosphorylation of eNOS in 5% O 2 was Ca 2+ -sensitive and reversed by okadaic acid or PP2A-C siRNA. The present findings establish that Ca 2+ mobilization stimulates both NO synthesis and PP2A-mediated eNOS dephosphorylation, thus constituting a novel negative feedback mechanism regulating eNOS activity not present in response to shear stress. This, coupled with enhanced NO bioavailability, underpins differences in NO signaling induced by inflammatory and physiologic stimuli that are apparent only in physiologic O 2 levels. Furthermore, an explicit delineation between physiologic normoxia and genuine hypoxia is defined here, with implications for our understanding of pathophysiological hypoxia.-Keeley, T. P., Siow, R. C. M., Jacob, R., Mann, G. E. A PP2A-mediated feedback mechanism controls Ca 2+ -dependent NO synthesis under physiological oxygen. © The Author(s).

Thermal O-H Bond Activation of Water as Mediated by Heteronuclear [Al2Mg2O5]•+: Evidence for Oxygen-Atom Scrambling.

PubMed

Geng, Caiyun; Li, Jilai; Weiske, Thomas; Schwarz, Helmut

2018-06-25

Mechanistic insight into the thermal O-H bond activation of water by the cubane-like, prototypical heteronuclear oxide cluster [Al 2 Mg 2 O 5 ] •+ has been derived from a combined experimental/computational study. Experiments in the highly diluted gas phase using Fourier transform ion-cyclotron resonance mass spectrometry show that hydrogen-atom abstraction from water by the cluster cation [Al 2 Mg 2 O 5 ] •+ occurs at ambient conditions accompanied by the liberation of an OH • radical. Due to a complete randomization of all oxygen atoms prior to fragmentation about 83% of the oxygen atoms of the hydroxyl radical released originate from the oxide cluster itself. The experimental findings are supported by detailed high-level quantum chemical calculations. The theoretical analysis reveals that the transfer of a formal hydrogen atom from water to the metal-oxide cation can proceed mechanistically via proton- or hydrogen-atom transfer exploiting different active sites of the cluster oxide. In addition to the unprecedented oxygen-atom scrambling, one of the more general and quite unexpected findings concerns the role of spin density at the hydrogen-acceptor oxide atom. While this feature is so crucial for [M-O] + /CH 4 couples, it is much less important in the O-H bond activation of water.

Physical activity and metabolic risk among US youth: Mediation by obesity [abstract

USDA-ARS?s Scientific Manuscript database

Physical activity has been inversely associated with metabolic risk, although pediatric studies are limited. It has been hypothesized that obesity mediates this relationship. Some studies reported that waist circumference (WC) is more highly related to metabolic risk than BMI, and may be a better me...

Understanding the Irradiation Behavior of Zirconium Carbide

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

Motta, Arthur; Sridharan, Kumar; Morgan, Dane

2013-10-11

Zirconium carbide (ZrC) is being considered for utilization in high-temperature gas-cooled reactor fuels in deep-burn TRISO fuel. Zirconium carbide possesses a cubic B1-type crystal structure with a high melting point, exceptional hardness, and good thermal and electrical conductivities. The use of ZrC as part of the TRISO fuel requires a thorough understanding of its irradiation response. However, the radiation effects on ZrC are still poorly understood. The majority of the existing research is focused on the radiation damage phenomena at higher temperatures (>450{degree}C) where many fundamental aspects of defect production and kinetics cannot be easily distinguished. Little is known aboutmore » basic defect formation, clustering, and evolution of ZrC under irradiation, although some atomistic simulation and phenomenological studies have been performed. Such detailed information is needed to construct a model describing the microstructural evolution in fast-neutron irradiated materials that will be of great technological importance for the development of ZrC-based fuel. The goal of the proposed project is to gain fundamental understanding of the radiation-induced defect formation in zirconium carbide and irradiation response by using a combination of state-of-the-art experimental methods and atomistic modeling. This project will combine (1) in situ ion irradiation at a specialized facility at a national laboratory, (2) controlled temperature proton irradiation on bulk samples, and (3) atomistic modeling to gain a fundamental understanding of defect formation in ZrC. The proposed project will cover the irradiation temperatures from cryogenic temperature to as high as 800{degree}C, and dose ranges from 0.1 to 100 dpa. The examination of this wide range of temperatures and doses allows us to obtain an experimental data set that can be effectively used to exercise and benchmark the computer calculations of defect properties. Combining the examination of radiation

Rosacea, reactive oxygen species, and azelaic Acid.

PubMed

Jones, David A

2009-01-01

Rosacea is a common skin condition thought to be primarily an inflammatory disorder. Neutrophils, in particular, have been implicated in the inflammation associated with rosacea and mediate many of their effects through the release of reactive oxygen species. Recently, the role of reactive oxygen species in the pathophysiology of rosacea has been recognized. Many effective agents for rosacea, including topical azelaic acid and topical metronidazole, have anti-inflammatory properties. in-vitro models have demonstrated the potent antioxidant effects of azelaic acid, providing a potential mechanistic explanation for its efficacy in the treatment of rosacea.

Retrospective Analysis Comparing Hollow Fiber and Silicone Membrane Oxygenators for Neonates on ECMO

PubMed Central

Mejak, Brian; Giacomuzzi, Carmen; Heller, Eileen; You, Xiaomang; Ungerleider, Ross; Shen, Irving

2007-01-01

Abstract: There is little information showing the use of microporous polypropylene hollow fiber oxygenators during extracorporeal life support (ECLS). Recent surveys have shown increasing use of these hollow fibers amongst ECLS centers in the United States. We performed a retrospective analysis comparing the Terumo BabyRx hollow fiber oxygenator to the Medtronic 800 silicone membrane oxygenator on 14 neonatal patients on extracorporeal membrane oxygenation (ECMO). The aim of this study was to investigate the similarities and differences when comparing pressure drops, prime volumes, oxygenator endurance, and gas transfer capabilities between the two groups. PMID:17672186

Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

NASA Technical Reports Server (NTRS)

Good, Brian S.

2015-01-01

Ytterbium disilicate is of interest as a potential environmental barrier coating for aerospace applications, notably for use in next generation jet turbine engines. In such applications, the transport of oxygen and water vapor through these coatings to the ceramic substrate is undesirable if high temperature oxidation is to be avoided. In an effort to understand the diffusion process in these materials, we have performed kinetic Monte Carlo simulations of vacancy-mediated and interstitial oxygen diffusion in Ytterbium disilicate. Oxygen vacancy and interstitial site energies, vacancy and interstitial formation energies, and migration barrier energies were computed using Density Functional Theory. We have found that, in the case of vacancy-mediated diffusion, many potential diffusion paths involve large barrier energies, but some paths have barrier energies smaller than one electron volt. However, computed vacancy formation energies suggest that the intrinsic vacancy concentration is small. In the case of interstitial diffusion, migration barrier energies are typically around one electron volt, but the interstitial defect formation energies are positive, with the result that the disilicate is unlikely to exhibit experience significant oxygen permeability except at very high temperature.

High temperature, low-cycle fatigue of copper-base alloys in argon. Part 2: Zirconium-copper at 482, 538 and 593 C

NASA Technical Reports Server (NTRS)

Conway, J. B.; Stentz, R. H.; Berling, J. T.

1973-01-01

Zirconium-copper (1/2 hard) was tested in argon over the temperature range from 482 to 593 C in an evaluation of short-term tensile and low-cycle fatigue behavior. The effect of strain rate on the tensile properties was evaluated at 538 C and in general it was found that the yield and ultimate strengths increased as the strain rate was increased from 0.0004 to 0.01/sec. Ductility was essentially insensitive to strain rate in the case of the zirconium-copper alloy. Strain-rate and hold-time effects on the low cycle fatigue behavior of zirconium-copper were evaluated in argon at 538 C. These effects were as expected in that decreased fatigue life was noted as the strain rate decreased and when hold times were introduced into the tension portion of the strain-cycle. Hold times in compression were much less detrimental than hold times in tension.

The chemistry of PET imaging with zirconium-89.

PubMed

Dilworth, Jonathan R; Pascu, Sofia I

2018-04-23

This Tutorial Review aims to provide an overview of the use of zirconium-89 complexes in biomedical imaging. Over the past decade there have been many new papers in this field, ranging from chemistry through to preclinical and clinical applications. Here we attempt to summarise the main developments that have occurred in this period. The primary focus is on coordination chemistry but other aspects such as isotope production, isotope properties, handling and radiochemical techniques and characterisation of cold and labelled complexes are included. Selected results from animal and human clinical studies are presented in the context of the stabilities and properties of the labelled bioconjugates.

Zirconium doped nano-dispersed oxides of Fe, Al and Zn for destruction of warfare agents

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

Stengl, Vaclav, E-mail: stengl@uach.cz; Houskova, Vendula; Bakardjieva, Snejana

2010-11-15

Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3'-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr{sup 4+} dopant can increase both the surface area and the surface hydroxylation of the resultingmore » doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr{sup 4+} converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr-FeO(OH) - being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions - exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.« less

Enhancement of C2C12 differentiation by perfluorocarbon-mediated oxygen delivery.

PubMed

Fujita, Hideaki; Shimizu, Kazunori; Morioka, Yuki; Nagamori, Eiji

2010-09-01

We have studied the effect of enhanced oxygen delivery by perfluorocarbons on the differentiation of C2C12 cells. The extent of differentiation was assessed by means of phase contrast/fluorescence microscopy, active tension measurement and the glucose consumption/lactate production rates. We found that enhanced oxygen delivery is suitable for full differentiation of C2C12 cells. Copyright 2010 The Society for Biotechnology, Japan. All rights reserved.

Squishy nanotraps: hybrid cellulose nanocrystal-zirconium metallogels for controlled trapping of biomacromolecules.

PubMed

Sheikhi, A; van de Ven, T G M

2017-08-11

A brick-and-mortar-like ultrasoft nanocomposite metallogel is formed by crosslinking cellulose nanocrystals (CNC) with ammonium zirconium carbonate (AZC) to trap and reconfigure dextran, a model biomacromolecule. The bricks (CNC) reinforce the metallogel, compete with dextran in reacting with AZC, and decouple long-time dextran dynamics from network formation, while the mortar (AZC) imparts bimodality to the dextran diffusion.

Eicosanoid-mediated immunity in insects

USDA-ARS?s Scientific Manuscript database

Eicosanoid is a collective term for oxygenated metabolites of C20 polyunsaturated fatty acids. As seen in mammals, eicosanoids play crucial roles in mediating various physiological processes, including immune responses, in insects. Upon microbial pathogen infection, non-self recognition signals are ...

A sputtering derived atomic oxygen source for studying fast atom reactions

NASA Technical Reports Server (NTRS)

Ferrieri, Richard A.; Yung, Y. Chu; Wolf, Alfred P.

1987-01-01

A technique for the generation of fast atomic oxygen was developed. These atoms are created by ion beam sputtering from metal oxide surfaces. Mass resolved ion beams at energies up to 60 KeV are produced for this purpose using a 150 cm isotope separator. Studies have shown that particles sputtered with 40 KeV Ar(+) on Ta2O5 were dominantly neutral and exclusively atomic. The atomic oxygen also resided exclusively in its 3P ground state. The translational energy distribution for these atoms peaked at ca 7 eV (the metal-oxygen bond energy). Additional measurements on V2O5 yielded a bimodal distribution with the lower energy peak at ca 5 eV coinciding reasonably well with the metal-oxygen bond energy. The 7 eV source was used to investigate fast oxygen atom reactions with the 2-butene stereoisomers. Relative excitation functions for H-abstraction and pi-bond reaction were measured with trans-2-butene. The abstraction channel, although of minor relative importance at thermal energy, becomes comparable to the addition channel at 0.9 eV and dominates the high-energy regime. Structural effects on the specific channels were also found to be important at high energy.

Development of sensors for monitoring oxygen and free radicals in plant physiology

NASA Astrophysics Data System (ADS)

Chaturvedi, Prachee

Oxygen plays a critical role in the physiology of photosynthetic organisms, including bioenergetics, metabolism, development, and stress response. Oxygen levels affect photosynthesis, respiration, and alternative oxidase pathways. Likewise, the metabolic rate of spatially distinct plant cells (and therefore oxygen flux) is known to be affected by biotic stress (e.g., herbivory) and environmental stress (e.g., salt/nutrient stress). During aerobic metabolism, cells produce reactive oxygen species (ROS) as a by product. Plants also produce ROS during adaptation to stress (e.g., abscisic acid (ABA) mediated stress responses). If stress conditions are prolonged, ROS levels surpass the capacity of detoxifying mechanisms within the cell, resulting in oxidative damage. While stress response pathways such as ABA-mediated mechanisms have been well characterized (e.g., water stress, inhibited shoot growth, synthesis of storage proteins in seeds), the connection between ROS production, oxygen metabolism and stress response remains unknown. In part, this is because details of oxygen transport at the interface of cell(s) and the surrounding microenvironment remains nebulous. The overall goal of this research was to develop oxygen and Free radical sensors for studying stress signaling in plants. Recent developments in nanomaterials and data acquisition systems were integrated to develop real-time, non-invasive oxygen and Free radical sensors. The availability of these sensors for plant physiologists is an exciting opportunity to probe the functional realm of cells and tissues in ways that were not previously possible.

Corrosion-electrochemical behavior of zirconium in molten alkali metal carbonates

NASA Astrophysics Data System (ADS)

Nikitina, E. V.

2016-08-01

The corrosion and electrochemical characteristics of zirconium during its interaction with molten lithium, sodium, and potassium carbonates containing from 1 to 5 wt % additives to the salt phase are studied in a temperature range of 500-800°C using gravimetry, corrosion potential measurement, and anodic polarization. The substances decreasing the corrosion losses due to the strengthening and thickening of an oxide film (lithium, sodium, potassium hydroxides) are used as passivators. Sodium chloride, fluoride, and sulfate serve as corrosion stimulators (activators).

Effect of Copper and Zirconium Addition on Properties of Fe-Co-Si-B-Nb Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Ikram, Haris; Khalid, Fazal Ahmad; Akmal, Muhammad; Abbas, Zameer

2017-07-01

In this research work, iron-based bulk metallic glasses (BMGs) have been fabricated, characterized and compared with Fe-Si alloy. BMG alloys of composition ((Fe0.6Co0.4)0.75B0.20Si0.05)96Nb4) were synthesized by suction casting technique using chilled copper die. Effect of copper and zirconium addition on magnetic, mechanical, thermal and electrochemical behavior of ((Fe0.6Co0.4)0.75B0.20Si0.05)96Nb4 BMGs was investigated. Furthermore, effect of annealing on nano-crystallization and subsequently on magnetic and mechanical behavior was also analyzed. Amorphousness of structure was evidenced by XRD analysis and microscopic visualization, whereas nano-crystallization behavior was identified by peak broadening of XRD patterns. Magnetic properties, measured by vibrating sample magnetometer, were found to be improved for as-cast BMG alloys by copper addition and further enhanced by nano-crystallization after annealing. Mechanical properties were observed to be increased by zirconium addition while slightly declined by copper addition. Potentiodynamic polarization analysis manifested the positive role of zirconium in enhancing corrosion resistance of BMGs in acidic, basic and brine mediums. Moreover, mechanical properties and corrosion analysis results affirmed the superiority of BMG alloys over Fe-Si alloy.

Oxygen Tension Within the Neurogenic Niche Regulates Dopaminergic Neurogenesis in the Developing Midbrain

PubMed Central

Wagenführ, Lisa; Meyer, Anne Karen; Marrone, Lara

2016-01-01

Oxygen tension is an important factor controlling stem cell proliferation and maintenance in various stem cell populations with a particular relevance in midbrain dopaminergic progenitors. Further studies have shown that the oxygen-dependent transcription factor hypoxia-inducible factor 1α (HIF-1α) is involved in these processes. However, all available studies on oxygen effects in dopaminergic neuroprogenitors were performed in vitro and thus it remains unclear whether tissue oxygen tension in the embryonic midbrain is also relevant for the regulation of dopaminergic neurogenesis in vivo. We thus dissect here the effects of oxygen tension in combination with HIF-1α conditional knockout on dopaminergic neurogenesis by using a novel experimental design allowing for the control of oxygen tension within the microenvironment of the neurogenic niche of the murine fetal midbrain in vivo. The microenvironment of the midbrain dopaminergic neurogenic niche was detected as hypoxic with oxygen tensions below 1.1%. Maternal oxygen treatment of 10%, 21%, and 75% atmospheric oxygen tension for 48 h translates into robust changes in fetal midbrain oxygenation. Fetal midbrain hypoxia hampered the generation of dopaminergic neurons and is accompanied with restricted fetal midbrain development. In contrast, induced hyperoxia stimulated proliferation and differentiation of dopaminergic progenitors during early and late embryogenesis. Oxygen effects were not directly mediated through HIF-1α signaling. These data—in agreement with in vitro data—indicate that oxygen is a crucial regulator of developmental dopaminergic neurogenesis. Our study provides the initial framework for future studies on molecular mechanisms mediating oxygen regulation of dopaminergic neurogenesis within the fetal midbrain as its natural environment. PMID:26577812

Pressure-induced kinetics of the α to ω transition in zirconium

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

Jacobsen, M. K.; Velisavljevic, N., E-mail: nenad@lanl.gov; Sinogeikin, S. V.

Diamond anvil cells (DAC) coupled with x-ray diffraction (XRD) measurements are one of the primary techniques for investigating structural stability of materials at high pressure-temperature (P-T) conditions. DAC-XRD has been predominantly used to resolve structural information at set P-T conditions and, consequently, provides P-T phase diagram information on a broad range of materials. With advances in large scale synchrotron x-ray facilities and corresponding x-ray diagnostic capabilities, it is now becoming possible to perform sub-second time resolved measurements on micron sized DAC samples. As a result, there is an opportunity to gain valuable information about the kinetics of structural phase transformationsmore » and extend our understanding of material behavior at high P-T conditions. Using DAC-XRD time resolved measurements, we have investigated the kinetics of the α to ω transformation in zirconium. We observe a clear time and pressure dependence in the martensitic α-ω transition as a function of pressure-jump, i.e., drive pressure. The resulting data are fit using available kinetics models, which can provide further insight into transformation mechanism that influence transformation kinetics. Our results help shed light on the discrepancies observed in previous measurements of the α-ω transition pressure in zirconium.« less

Pressure-induced kinetics of the α to ω transition in zirconium

DOE PAGES

Jacobsen, M. K.; Velisavljevic, N.; Sinogeikin, S. V.

2015-07-13

Diamond anvil cells (DAC) coupled with x-ray diffraction (XRD) measurements are one of the primary techniques for investigating structural stability of materials at high pressure-temperature (P-T) conditions. DAC-XRD has been predominantly used to resolve structural information at set P-T conditions and, consequently, provides P-T phase diagram information on a broad range of materials. With advances in large scale synchrotron x-ray facilities and corresponding x-ray diagnostic capabilities, it is now becoming possible to perform sub-second time resolved measurements on micron sized DAC samples. As a result, there is an opportunity to gain valuable information about the kinetics of structural phase transformationsmore » and extend our understanding of material behavior at high P-T conditions. Using DAC-XRD time resolved measurements, we have investigated the kinetics of the α to ω transformation in zirconium. We observe a clear time and pressure dependence in the martensitic α-ω transition as a function of pressure-jump, i.e., drive pressure. The resulting data are fit using available kinetics models, which can provide further insight into transformation mechanism that influence transformation kinetics. Our results help shed light on the discrepancies observed in previous measurements of the α-ω transition pressure in zirconium.« less

Oxygen-conserving reflexes of the brain: the current molecular knowledge.

PubMed

Schaller, B; Cornelius, J F; Sandu, N; Ottaviani, G; Perez-Pinzon, M A

2009-04-01

The trigemino-cardiac reflex (TCR) may be classified as a sub-phenomenon in the group of the so-called 'oxygen-conserving reflexes'. Within seconds after the initiation of such a reflex, there is neither a powerful and differentiated activation of the sympathetic system with subsequent elevation in regional cerebral blood flow (CBF) with no changes in the cerebral metabolic rate of oxygen (CMRO(2)) or in the cerebral metabolic rate of glucose (CMRglc). Such an increase in regional CBF without a change of CMRO(2) or CMRglc provides the brain with oxygen rapidly and efficiently and gives substantial evidence that the TCR is an oxygen-conserving reflex. This system, which mediates reflex protection projects via currently undefined pathways from the rostral ventrolateral medulla oblongata to the upper brainstem and/or thalamus which finally engage a small population of neurons in the cortex. This cortical centre appears to be dedicated to reflexively transduce a neuronal signal into cerebral vasodilatation and synchronization of electrocortical activity. Sympathetic excitation is mediated by cortical-spinal projection to spinal pre-ganglionic sympathetic neurons whereas bradycardia is mediated via projections to cardiovagal motor medullary neurons. The integrated reflex response serves to redistribute blood from viscera to brain in response to a challenge to cerebral metabolism, but seems also to initiate a preconditioning mechanism. Better and more detailed knowledge of the cascades, transmitters and molecules engaged in such endogenous (neuro) protection may provide new insights into novel therapeutic options for a range of disorders characterized by neuronal death and into cortical organization of the brain.

Hydrogen atom abstraction from aldehydes - OH + H2CO and O + H2CO

NASA Technical Reports Server (NTRS)

Dupuis, M.; Lester, W. A., Jr.

1984-01-01

The essential features of the potential energy surfaces governing hydrogen abstraction from formaldehyde by oxygen atom and hydroxyl radical have been characterized with ab inito multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) wave functions. The results are consistent with a very small activation energy for the OH + H2CO reaction, and an activation energy of a few kcal/mol for the O + H2CO reaction. In the transition state structure of both systems, the attacking oxygen atom is nearly collinear with the attacked CH bond.

Possibilities of surface coating for thermal insulation. [zirconium dioxide, titanium dioxide, and zircon coatings

NASA Technical Reports Server (NTRS)

Poeschel, E.; Weisser, G.

1979-01-01

Calculations performed for pulsating heat sources indicate a relatively thin (200-1000 micron) coating can lower temperature both inside and on the surface of a construction material. Various coating materials (including zirconium dioxide) are discussed, together with possible thermic stresses and ways to deal with the latter.

Renal Carcinogenesis, Tumor Heterogeneity, and Reactive Oxygen Species: Tactics Evolved

PubMed Central

Shanmugasundaram, Karthigayan

2016-01-01

Abstract Significance: The number of kidney cancers is growing 3–5% each year due to unknown etiologies. Intra- and inter-tumor mediators increase oxidative stress and drive tumor heterogeneity. Recent Advances: Technology advancement in state-of-the-art instrumentation and methodologies allows researchers to detect and characterize global landscaping modifications in genes, proteins, and pathophysiology patterns at the single-cell level. Critical Issues: We postulate that the sources of reactive oxygen species (ROS) and their activation within subcellular compartments will change over a timeline of tumor evolvement and contribute to tumor heterogeneity. Therefore, the complexity of intracellular changes within a tumor and ROS-induced tumor heterogeneity coupled to the advancement of detecting these events globally are limited at the level of data collection, organization, and interpretation using software algorithms and bioinformatics. Future Directions: Integrative and collaborative research, combining the power of numbers with careful experimental design, protocol development, and data interpretation, will translate cancer biology and therapeutics to a heightened level or leave the abundant raw data as stagnant and underutilized. Antioxid. Redox Signal. 25, 685–701. PMID:27287984

Large-scale self-assembled zirconium phosphate smectic layers via a simple spray-coating process

NASA Astrophysics Data System (ADS)

Wong, Minhao; Ishige, Ryohei; White, Kevin L.; Li, Peng; Kim, Daehak; Krishnamoorti, Ramanan; Gunther, Robert; Higuchi, Takeshi; Jinnai, Hiroshi; Takahara, Atsushi; Nishimura, Riichi; Sue, Hung-Jue

2014-04-01

The large-scale assembly of asymmetric colloidal particles is used in creating high-performance fibres. A similar concept is extended to the manufacturing of thin films of self-assembled two-dimensional crystal-type materials with enhanced and tunable properties. Here we present a spray-coating method to manufacture thin, flexible and transparent epoxy films containing zirconium phosphate nanoplatelets self-assembled into a lamellar arrangement aligned parallel to the substrate. The self-assembled mesophase of zirconium phosphate nanoplatelets is stabilized by epoxy pre-polymer and exhibits rheology favourable towards large-scale manufacturing. The thermally cured film forms a mechanically robust coating and shows excellent gas barrier properties at both low- and high humidity levels as a result of the highly aligned and overlapping arrangement of nanoplatelets. This work shows that the large-scale ordering of high aspect ratio nanoplatelets is easier to achieve than previously thought and may have implications in the technological applications for similar materials.

Studies of anti-fibrillogenic activity of phthalocyanines of zirconium containing out-of-plane ligands.

PubMed

Kovalska, Vladyslava; Losytskyy, Mykhaylo; Chernii, Viktor; Volkova, Kateryna; Tretyakova, Iryna; Cherepanov, Vsevolod; Yarmoluk, Sergiy; Volkov, Sergiy

2012-01-01

Series of phthalocyanines of zirconium containing lysine, citric, nonanoic acid residues and dibenzolylmethane groups as out-of-plane ligands are firstly studied as inhibitors of fibrillogenesis using cyanine-based fluorescent inhibitory assay. It was shown that studied phthalocyanines at concentration of 20μM inhibited aggregation reaction on 38.5-57.6% and inhibitory activity of phthalocyanines depended on the chemical nature of out-of-plane ligand. For the most active compound PcZrLys(2) (zirconium phthalocyanine containing lysine fragment) the efficient inhibitor concentration was estimated to be 37μM. AFM studies have shown that in the presence of PcZrLys(2) the inhibition of fibrils formation and formation of spherical oligomeric aggregates took place. Due to the ability of phthalocyanines to decrease efficiently protein aggregation into the amyloid fibrils, modification of phthalocyanine molecules via out-of-plane substitutions was proposed as approach for design of anti-fibrillogenic agents with required properties. Copyright © 2011. Published by Elsevier Ltd.

High pressure low temperature hot pressing method for producing a zirconium carbide ceramic

DOEpatents

Cockeram, Brian V.

2017-01-10

A method for producing monolithic Zirconium Carbide (ZrC) is described. The method includes raising a pressure applied to a ZrC powder until a final pressure of greater than 40 MPa is reached; and raising a temperature of the ZrC powder until a final temperature of less than 2200.degree. C. is reached.

An investigation on the preparation of nanocrystalline hydrous zirconia from zirconium tungstate

NASA Astrophysics Data System (ADS)

Antunes, M.; Perottoni, C. A.; Gouvêa, D.; Machado, G.; Zorzi, J. E.

2018-02-01

Hydrous nanocrystalline zirconia was prepared from an unusual precursor—the bimetallic oxide zirconium tungstate (ZrW2O8)—in alkaline medium. Different experimental conditions (NaOH concentration, time and temperature) were used to investigate the effects on crystallographic, morphological, chemical and thermal characteristics of the products. The resulting materials are composed of particles with a crystal structure similar to that of cubic ZrO2 (or a mixture of tetragonal and cubic phases, depending on the synthesis conditions), with particle size around 5 nm and crystallites around 3 nm in diameter. These particles form high surface area agglomerates, exhibiting mesoporosity and capacity for adsorption of water and carbon dioxide. The synthesis mechanism appears to be constituted, first, by a chemical substitution reaction between the WO4 tetrahedra and hydroxyl ions, with subsequent solubilization of the structure. Indeed, excess hydroxyls in the medium form colloidal zirconium ions which polymerize/condense, generating crystalline nuclei in a process facilitated by heterogeneous nucleation and supersaturation. The presence of residual tungsten in all samples appears to be a key element for stabilizing the size and crystalline structure of the materials produced.

Optimal aluminum/zirconium: Protein interactions for predicting antiperspirant efficacy using zeta potential measurements.

PubMed

Yuan, Shaotang; Vaughn, John; Pappas, Iraklis; Fitzgerald, Michael; Masters, James G; Pan, Long

2015-01-01

The interactions between commercial antiperspirant (AP) salts [aluminum chlorohydrate (ACH), activated ACH, aluminum sesquichlorohydrate (ASCH), zirconium aluminum glycine (ZAG), activated ZAG), pure aluminum polyoxocations (Al13-mer, Al30-mer), and the zirconium(IV)-glycine complex Zr6 (O)4 (OH)4 (H2O)8 (Gly)8]12+(-) (CP-2 or ZG) with Bovine serum albumin (BSA) were studied using zeta potential and turbidity measurements. The maximal turbidity, which revealed the optimal interactions between protein and metal salts, for all protein-metal salt samples was observed at the isoelectric point (IEP), where the zeta potential of the solution was zero. Efficacy of AP salts was determined via three parameters: the amount of salt required to flocculate BSA to reach IEP, the turbidity of solution at the IEP, and the pH range over which the turbidity of the solution remains sufficiently high. By comparing active salt performance from this work to traditional prescreening methods, this methodology was able to provide a consistent efficacy assessment for metal actives in APs or in water treatment.

Numerical Simulations on the Laser Spot Welding of Zirconium Alloy Endplate for Nuclear Fuel Bundle Assembly

NASA Astrophysics Data System (ADS)

Satyanarayana, G.; Narayana, K. L.; Boggarapu, Nageswara Rao

2018-03-01

In the nuclear industry, a critical welding process is joining of an end plate to a fuel rod to form a fuel bundle. Literature on zirconium welding in such a critical operation is limited. A CFD model is developed and performed for the three-dimensional non-linear thermo-fluid analysis incorporating buoyancy and Marnangoni stress and specifying temperature dependent properties to predict weld geometry and temperature field in and around the melt pool of laser spot during welding of a zirconium alloy E110 endplate with a fuel rod. Using this method, it is possible to estimate the weld pool dimensions for the specified laser power and laser-on-time. The temperature profiles will estimate the HAZ and microstructure. The adequacy of generic nature of the model is validated with existing experimental data.

In situ DRIFTS investigation of NH3-SCR reaction over CeO2/zirconium phosphate catalyst

NASA Astrophysics Data System (ADS)

Zhang, Qiulin; Fan, Jie; Ning, Ping; Song, Zhongxian; Liu, Xin; Wang, Lanying; Wang, Jing; Wang, Huimin; Long, Kaixian

2018-03-01

A series of ceria modified zirconium phosphate catalysts were synthesized for selective catalytic reduction of NO with ammonia (NH3-SCR). Over 98% NOx conversion and 98% N2 selectivity were obtained by the CeO2/ZrP catalyst with 20 wt.% CeO2 loading at 250-425 °C. The interaction between CeO2 and zirconium phosphate enhanced the redox abilities and surface acidities of the catalysts, resulting in the improvement of NH3-SCR activity. The in situ DRIFTS results indicated that the NH3-SCR reaction over the catalysts followed both Eley-Rideal and Langmuir-Hinshelwood mechanisms. The amide (sbnd NH2) groups and the NH4+ bonded to Brønsted acid sites were the important intermediates of Eley-Rideal mechanism.

Lysophosphatidic acid induces reactive oxygen species generation by activating protein kinase C in PC-3 human prostate cancer cells

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

Lin, Chu-Cheng; Lin, Chuan-En; Lin, Yueh-Chien

2013-11-01

Highlights: •LPA induces ROS generation through LPA{sub 1} and LPA{sub 3}. •LPA induces ROS generation by activating PLC. •PKCζ mediates LPA-induced ROS generation. -- Abstract: Prostate cancer is one of the most frequently diagnosed cancers in males, and PC-3 is a cell model popularly used for investigating the behavior of late stage prostate cancer. Lysophosphatidic acid (LPA) is a lysophospholipid that mediates multiple behaviors in cancer cells, such as proliferation, migration and adhesion. We have previously demonstrated that LPA enhances vascular endothelial growth factor (VEGF)-C expression in PC-3 cells by activating the generation of reactive oxygen species (ROS), which ismore » known to be an important mediator in cancer progression. Using flow cytometry, we showed that LPA triggers ROS generation within 10 min and that the generated ROS can be suppressed by pretreatment with the NADPH oxidase (Nox) inhibitor diphenylene iodonium. In addition, transfection with LPA{sub 1} and LPA{sub 3} siRNA efficiently blocked LPA-induced ROS production, suggesting that both receptors are involved in this pathway. Using specific inhibitors and siRNA, phospholipase C (PLC) and protein kinase C (PKC) were also suggested to participate in LPA-induced ROS generation. Overall, we demonstrated that LPA induces ROS generation in PC-3 prostate cancer cells and this is mediated through the PLC/PKC/Nox pathway.« less

Exposure of Bacterial Biofilms to Electrical Current Leads to Cell Death Mediated in Part by Reactive Oxygen Species

PubMed Central

Brinkman, Cassandra L.; Schmidt-Malan, Suzannah M.; Karau, Melissa J.; Greenwood-Quaintance, Kerryl; Hassett, Daniel J.; Mandrekar, Jayawant N.

2016-01-01

Bacterial biofilms may form on indwelling medical devices such as prosthetic joints, heart valves and catheters, causing challenging-to-treat infections. We have previously described the ‘electricidal effect’, in which bacterial biofilms are decreased following exposure to direct electrical current. Herein, we sought to determine if the decreased bacterial quantities are due to detachment of biofilms or cell death and to investigate the role that reactive oxygen species (ROS) play in the observed effect. Using confocal and electron microscopy and flow cytometry, we found that direct current (DC) leads to cell death and changes in the architecture of biofilms formed by Gram-positive and Gram-negative bacteria. Reactive oxygen species (ROS) appear to play a role in DC-associated cell death, as there was an increase in ROS-production by Staphylococcus aureus and Staphylococcus epidermidis biofilms following exposure to DC. An increase in the production of ROS response enzymes catalase and superoxide dismutase (SOD) was observed for S. aureus, S. epidermidis and Pseudomonas aeruginosa biofilms following exposure to DC. Additionally, biofilms were protected from cell death when supplemented with antioxidants and oxidant scavengers, including catalase, mannitol and Tempol. Knocking out SOD (sodAB) in P. aeruginosa led to an enhanced DC effect. Microarray analysis of P. aeruginosa PAO1 showed transcriptional changes in genes related to the stress response and cell death. In conclusion, the electricidal effect results in death of bacteria in biofilms, mediated, at least in part, by production of ROS. PMID:27992529

Exposure of Bacterial Biofilms to Electrical Current Leads to Cell Death Mediated in Part by Reactive Oxygen Species.

PubMed

Brinkman, Cassandra L; Schmidt-Malan, Suzannah M; Karau, Melissa J; Greenwood-Quaintance, Kerryl; Hassett, Daniel J; Mandrekar, Jayawant N; Patel, Robin

2016-01-01

Bacterial biofilms may form on indwelling medical devices such as prosthetic joints, heart valves and catheters, causing challenging-to-treat infections. We have previously described the 'electricidal effect', in which bacterial biofilms are decreased following exposure to direct electrical current. Herein, we sought to determine if the decreased bacterial quantities are due to detachment of biofilms or cell death and to investigate the role that reactive oxygen species (ROS) play in the observed effect. Using confocal and electron microscopy and flow cytometry, we found that direct current (DC) leads to cell death and changes in the architecture of biofilms formed by Gram-positive and Gram-negative bacteria. Reactive oxygen species (ROS) appear to play a role in DC-associated cell death, as there was an increase in ROS-production by Staphylococcus aureus and Staphylococcus epidermidis biofilms following exposure to DC. An increase in the production of ROS response enzymes catalase and superoxide dismutase (SOD) was observed for S. aureus, S. epidermidis and Pseudomonas aeruginosa biofilms following exposure to DC. Additionally, biofilms were protected from cell death when supplemented with antioxidants and oxidant scavengers, including catalase, mannitol and Tempol. Knocking out SOD (sodAB) in P. aeruginosa led to an enhanced DC effect. Microarray analysis of P. aeruginosa PAO1 showed transcriptional changes in genes related to the stress response and cell death. In conclusion, the electricidal effect results in death of bacteria in biofilms, mediated, at least in part, by production of ROS.

Antiangiogenic effect of betaine on pathologic retinal neovascularization via suppression of reactive oxygen species mediated vascular endothelial growth factor signaling.

PubMed

Park, Sung Wook; Jun, Hyoung Oh; Kwon, Euna; Yun, Jun-Won; Kim, Jin Hyoung; Park, Young-Jun; Kang, Byeong-Cheol; Kim, Jeong Hun

2017-03-01

Reactive oxygen species (ROS) as well as vascular endothelial growth factor (VEGF) play important roles in pathologic retinal neovascularization. We investigated whether betaine inhibits pathologic retinal neovascularization in a mouse model of oxygen induced retinopathy (OIR). Betaine was intravitreally injected in OIR mice at postnatal day (P) 14. At P17, the neovascular tufts area in OIR retina was analyzed. Intravitreal injection of betaine (200μM) effectively reduced the neovascular tufts area in OIR retina (68.0±6.7% of the control eyes, P<0.05). Even in a high concentration (2mM), betaine never induced any retinal toxicity or cytotoxicity. Betaine significantly inhibited VEGF-induced proliferation, migration, and tube formation in human retinal microvascular endothelial cells (HRMECs). Betaine suppressed VEGF-induced VEGFR-2, Akt and ERK phosphorylation in HRMECs. In human brain astrocytes, betaine reduced tBH-induced ROS production, and subsequently attenuated tBH-induced VEGFA mRNA transcription via suppression of ROS. Our data suggest that betaine has an anti-angiogenic effect on pathologic retinal neovascularization via suppression of ROS mediated VEGF signaling. Betaine could be a potent anti-angiogenic agent to treat pathologic retinal neovascularization. Copyright © 2016 Elsevier Inc. All rights reserved.

Di-macrocyclic terephthalamide ligands as chelators for the PET radionuclide zirconium-89

DOE PAGES

Pandya, Darpan N.; Pailloux, Sylvie; Tatum, David; ...

2014-12-18

The development of bifunctional chelators (BFCs) which can stably chelate zirconium-89 ((89)Zr) while being conjugated to targeting molecules is an area of active research. Herein we report the first octadentate terephthalamide ligands, which are easily radiolabeled with (89)Zr and are highly stable in vitro. Lastly, they represent a novel class of chelators, which are worthy of further development as BFCs for (89)Zr.

Blue-Light Inhibition of Listeria monocytogenes Growth Is Mediated by Reactive Oxygen Species and Is Influenced by σB and the Blue-Light Sensor Lmo0799

PubMed Central

O'Donoghue, Beth; NicAogáin, Kerrie; Bennett, Claire; Conneely, Alan; Tiensuu, Teresa; Johansson, Jörgen

2016-01-01

ABSTRACT Listeria monocytogenes senses blue light via the flavin mononucleotide-containing sensory protein Lmo0799, leading to activation of the general stress response sigma factor SigB (σB). In this study, we investigated the physiological response of this foodborne pathogen to blue light. We show that blue light (460 to 470 nm) doses of 1.5 to 2 mW cm−2 cause inhibition of growth on agar-based and liquid culture media. The inhibitory effects are dependent on cell density, with reduced effects evident when high cell numbers are present. The addition of 20 mM dimethylthiourea, a scavenger of reactive oxygen species, or catalase to the medium reverses the inhibitory effects of blue light, suggesting that growth inhibition is mediated by the formation of reactive oxygen species. A mutant strain lacking σB (ΔsigB) was found to be less inhibited by blue light than the wild type, likely indicating the energetic cost of deploying the general stress response. When a lethal dose of light (8 mW cm−2) was applied to cells, the ΔsigB mutant displayed a marked increase in sensitivity to light compared to the wild type. To investigate the role of the blue-light sensor Lmo0799, mutants were constructed that either had a deletion of the gene (Δlmo0799) or alteration in a conserved cysteine residue at position 56, which is predicted to play a pivotal role in the photocycle of the protein (lmo0799 C56A). Both mutants displayed phenotypes similar to the ΔsigB mutant in the presence of blue light, providing genetic evidence that residue 56 is critical for light sensing in L. monocytogenes. Taken together, these results demonstrate that L. monocytogenes is inhibited by blue light in a manner that depends on reactive oxygen species, and they demonstrate clear light-dependent phenotypes associated with σB and the blue-light sensor Lmo0799. IMPORTANCE Listeria monocytogenes is a bacterial foodborne pathogen that can cause life-threatening infections in humans. It is known to

Comparative Analysis of the Mechanical Properties between the Fiber-Reinforced Composite and Zirconium Posts.

PubMed

Jurukovska-Shotarovska, Vesna; Kapusevska, Biljana

2015-01-01

To make a comparative analysis of the mechanical properties between FRC and zirconium posts Methods: The patients with FRC and zirconium posts were divided in two groups with three subgroups, each of them composed of 10 samples. Subgroup I with 1.2 mm; Subgroup II with 1.35 mm and Subgroup III with 1.5 mm post diameter. The fracture force, bending and tensile strength of each group were measured with Shimadzu Universal Testing Machine. The fracture force for the first group measured in the first, second and third subgroup was 34.80900N; 67.15390N; 46.53100N and for the second group, first, second and third subgroup was 34.80900N; 46.53100N; 67.15390N correspondingly. The bending strength for the first group measured in the first, second and third subgroup was 401.4420N; 444.6425N; 333.6828N and for the second group, first, second and third subgroup was 307.9352N; 289.1030N; 304.1649N correspondingly. The tensile strength for the first group measured in the first, second and third subgroup was 5.442267N; 4.350545N; 2.943465N and for the second group, first, second and third subgroup was 4.224141N; 3.751466N; 3.168756N correspondingly. The longest diameter of the posts significantly increases the resistance to fracture in relation to the two smaller diameters. The larger diameter, the higher values of the bending strength, as well as the lowest values of the tensile strength of the material contribute to improved mechanical properties of the fiber and zirconium posts.

Influence of Ar-irradiation on structural and nanomechanical properties of pure zirconium measured by means of GIXRD and nanoindentation techniques

NASA Astrophysics Data System (ADS)

Kurpaska, L.; Gapinska, M.; Jasinski, J.; Lesniak, M.; Sitarz, M.; Nowakowska-Langier, K.; Jagielski, J.; Wozniak, K.

2016-12-01

An effect of Ar-irradiation on structural and nanomechanical properties of pure zirconium at room temperature was investigated. In order to simulate the radiation damage, the argon ions were implanted into the pure zirconium coupons with fluences ranging from 1 × 1015 to 1 × 1017 cm-2. Prior to irradiation, zirconium samples were chemically polished with a solution of HF/HNO3/H2O. Structural properties of the implanted layer were studied using Grazing Incidence X-Ray Diffraction (GIXRD) technique. The nanomechanical properties of the material were measured by means of nanoindentation technique. The obtained results revealed correlation between Ar-implantation fluence, hardness and structural properties (as confirmed by the modification of the diffraction peaks). Material hardening and peak shift & broadening in GIXD spectra were associated with the local increase of micro-strains, which is related to the increased density of type - dislocation loops. Presented study confirms that the structural changes induced by ion irradiation are directly linked to the mechanical response of the sample.

Electrochemical response of carbon paste electrode modified with mixture of titanium dioxide/zirconium dioxide in the detection of heavy metals: lead and cadmium.

PubMed

Nguyen, Phuong Khanh Quoc; Lunsford, Suzanne K

2012-11-15

A novel carbon modified electrode was developed by incorporating titanium dioxide/zirconium dioxide into the graphite carbon paste electrode to detect heavy metals-cadmium and lead. In this work, the development of the novel titanium dioxide/zirconium dioxide modified carbon paste electrode was studied to determine the optimum synthesis conditions related to the temperature, heating duration, amount and ratio of titanium dioxide/zirconium dioxide, and amount of surfactant, to create the most reproducible results. Using cyclic voltammetric (CV) analysis, this study has proven that the novel titanium dioxide/zirconium dioxide can be utilized to detect heavy metals-lead and cadmium, at relatively low concentrations (7.6×10(-6) M and 1.1×10(-5) M for Pb and Cd, respectively) at optimum pH value (pH=3). From analyzing CV data the optimal electrodes surface area was estimated to be 0.028 (±0.003) cm(2). Also, under the specific experimental conditions, electron transfer coefficients were estimated to be 0.44 and 0.33 along with the heterogeneous electron transfer rate constants of 5.64×10(-3) and 2.42×10(-3) (cm/s) for Pb and Cd, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Rosacea, Reactive Oxygen Species, and Azelaic Acid

PubMed Central

2009-01-01

Rosacea is a common skin condition thought to be primarily an inflammatory disorder. Neutrophils, in particular, have been implicated in the inflammation associated with rosacea and mediate many of their effects through the release of reactive oxygen species. Recently, the role of reactive oxygen species in the pathophysiology of rosacea has been recognized. Many effective agents for rosacea, including topical azelaic acid and topical metronidazole, have anti-inflammatory properties. in-vitro models have demonstrated the potent antioxidant effects of azelaic acid, providing a potential mechanistic explanation for its efficacy in the treatment of rosacea. PMID:20967185

Effect of anodization on the surface characteristics and electrochemical behaviour of zirconium in artificial saliva.

PubMed

Romonti, Daniela E; Gomez Sanchez, Andrea V; Milošev, Ingrid; Demetrescu, Ioana; Ceré, Silvia

2016-05-01

The paper is focused on elaboration of ZrO2 films on pure zirconium via anodizing in phosphoric acid with and without fluoride at constant potentials of 30 V and 60 V. The structure and composition of the films were investigated using scanning electronic microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The composition of the oxides formed at both potentials can be identified as monoclinic ZrO2. In addition to Zr and O, the layers formed in phosphoric acid contain phosphorus originating from the phosphoric acid. When the phosphoric acid solution contains NaF, fluorine is also incorporated into the oxide layer. The oxides formed at a higher voltage have greater roughness than those formed at 30 V. Anodized samples exhibit smaller current densities during anodic polarization compared to the as-received zirconium covered with native oxide. Copyright © 2016 Elsevier B.V. All rights reserved.

Cavity resonator for dielectric measurements of high-ɛ, low loss materials, demonstrated with barium strontium zirconium titanate ceramics

NASA Astrophysics Data System (ADS)

Marksteiner, Quinn R.; Treiman, Michael B.; Chen, Ching-Fong; Haynes, William B.; Reiten, M. T.; Dalmas, Dale; Pulliam, Elias

2017-06-01

A resonant cavity method is presented which can measure loss tangents and dielectric constants for materials with dielectric constant from 150 to 10 000 and above. This practical and accurate technique is demonstrated by measuring barium strontium zirconium titanate bulk ferroelectric ceramic blocks. Above the Curie temperature, in the paraelectric state, barium strontium zirconium titanate has a sufficiently low loss that a series of resonant modes are supported in the cavity. At each mode frequency, the dielectric constant and loss tangent are obtained. The results are consistent with low frequency measurements and computer simulations. A quick method of analyzing the raw data using the 2D static electromagnetic modeling code SuperFish and an estimate of uncertainties are presented.

Exposure of vitamins to UVB and UVA radiation generates singlet oxygen.

PubMed

Knak, Alena; Regensburger, Johannes; Maisch, Tim; Bäumler, Wolfgang

2014-05-01

Deleterious effects of UV radiation in tissue are usually attributed to different mechanisms. Absorption of UVB radiation in cell constituents like DNA causes photochemical reactions. Absorption of UVA radiation in endogenous photosensitizers like vitamins generates singlet oxygen via photosensitized reactions. We investigated two further mechanisms that might be involved in UV mediated cell tissue damage. Firstly, UVB radiation and vitamins also generate singlet oxygen. Secondly, UVB radiation may change the chemical structure of vitamins that may change the role of such endogenous photosensitizers in UVA mediated mechanisms. Vitamins were irradiated in solution using monochromatic UVB (308 nm) or UVA (330, 355, or 370 nm) radiation. Singlet oxygen was directly detected and quantified by its luminescence at 1270 nm. All investigated molecules generated singlet oxygen with a quantum yield ranging from 0.007 (vitamin D3) to 0.64 (nicotinamide) independent of the excitation wavelength. Moreover, pre-irradiation of vitamins with UVB changed their absorption in the UVB and UVA spectral range. Subsequently, molecules such as vitamin E and vitamin K1, which normally exhibit no singlet oxygen generation in the UVA, now produce singlet oxygen when exposed to UVA at 355 nm. This interplay of different UV sources is inevitable when applying serial or parallel irradiation with UVA and UVB in experiments in vitro. These results should be of particular importance for parallel irradiation with UVA and UVB in vivo, e.g. when exposing the skin to solar radiation.

Ammonium excretion and oxygen respiration of tropical copepods and euphausiids exposed to oxygen minimum zone conditions

NASA Astrophysics Data System (ADS)