The method of production of xAl{sub 2}O{sub 3}-yTiO{sub 2} compositions provides for the depth distribution of coating components and specifies its mechanical properties. In case of the composition obtained by cladding, titanium is mainly concentrated at the substrate. In case of mechanical mixture or composition obtained by sintering the oxides, the depth distribution of coating components is random.
It has been discovered that iron(III) chloride complexes supported on activated charcoal oxidize phosphine under normal conditions. The process accelerates as the concentration of the chloride ions and the proton acid increases.
Synergism has been observed during inhibiting initiated oxidation of styrene or tetralin by organic phosphites in the presence of complex compounds of some transition metals. The results are given of non-additive intensification of antioxidative activity of triphenylphosphite (TPP) and tri-(4-methyl-6-tert.-- butyl)-phenyl-phosphite (TMBP) in the process of initiated oxidation of styrene or tetralin with addition of acetylacetonates of cobalt and vanadyl. During styrene oxidation, inhibition of the reaction with chelate complex of vanadyl is weakened considerably when phosphite is added into the reaction system. During tetralin oxidation, postcatalytic (or branched) oxidation is observed only for large concentration of vanadyl complex. Addition of TPP to above complex sharply increases the induction ...
Chemical oxidation is a treatment technology that uses powertul chemical oxidizers to destroy organic contaminants. Typical oxidizers used in chemical oxidation processes include ozone, hydrogen peroxide, chlorine, and potassium permanganate. The chemical reaction products are usually simple organic compounds, such as carboxylic acids, and/or inorganic compounds, such as carbon dioxide, water, and simple inorganic complexes (e.g., chloride salts, in the case of chemical oxidation treatment of chlorinated solvents).
Reaction of At(I) with triphenylphosphine, triethylphosphite and tri-n-octylphosphine oxide was investigated in ethanolic solution by means of electromigration. A cationic complex with triphenylphosphine was identified being stable at pH = 1,9 in the concentration range of the ligand between c = 10{sup -5} to 10{sup -3} M. At a higher ligand concentration and at pH>2, the reduction effect of phosphine is superimposed on the complex formation. Complex formation is confirmed by ligand exchange reactions with Br{sup -} and I{sup -}. A comparatively weak complex is formed by triethylphosphite and At(I). No compound is formed by tri-n-octylphosphine oxide and At(I). (orig.).
Reaction of At(I) with triphenylphosphine, triethylphosphite and tri-n-octylphosphine oxide was investigated in ethanolic solution by means of electromigration. A cationic complex with triphenylphosphine was identified being stable at pH = 1,9 in the concentration range of the ligand between c = 10"-"5 to 10"-"3 M. At a higher ligand concentration and at pH>2, the reduction effect of phosphine is superimposed on the complex formation. Complex formation is confirmed by ligand exchange reactions with Br"- and I"-. A comparatively weak complex is formed by triethylphosphite and At(I). No compound is formed by tri-n-octylphosphine oxide and At(I). (orig.).
A number of amines can be employed for all volatile treatment (AVT) of steam generator (SG) systems of nuclear power reactors. These amines form complexes with Cu{sup 2+} and Ni{sup 2+} ions which come into water due to corrosion. The redox reactions of a number of Cu(II)-AVT amine complexes and the stability of the transient species formed have been studied by pulse radiolysis technique. Rate constants for the reaction of e{sub aq}{sup -} with a number of Cu(II)-amine complexes have been determined by following the decay of e{sub aq}{sup -} absorption. Stability of Cu(I)-amine complexes was studied by following the kinetics of the bleaching signal formed at the {lambda}{sub max} of the Cu(II) amine complex. Except for Cu(I)-triethanolamine complex all other Cu(I)-amine complexes were found to be stable. One-electron ...
New nanofibers containing poly(vinyl pyrrolidone)-iodine complex (PVP-iodine) were obtained by electrospinning in order to prepare materials suitable for wound dressings. Different approaches were used: a one-step method based on electrospinning of PVP-iodine or poly(ethylene oxide)/PVP-iodine solutions and a three-step method based on electrospinning of PVP or poly(ethylene oxide)/PVP mixed solutions followed by photo-mediated crosslinking of the obtained nanofibers and subsequent complexation with iodine. The average diameters of the fibers were in the range 150-470nm depending on the composition and on the applied field strength (AFS) and increased with increasing the amount of PEO in the spinning solutions. Higher AFS resulted in greater fiber diameter and in size distribution broadeni...
The monoanionic bidentate Schiff base, N-(phenolyl)-benzaldimine (HL), has been employed to synthesize a new vanadium(IV) complex of general composition [VO(L)2] (where L = O, N donor of Schiff base). The ligand and complex have been fully characterized by elemental analyses, molar conductance data, FT-IR, 1H- and 13C-NMR, and UV-Vis spectroscopies. Oxidation of alcohols to their corresponding aldehydes and ketones was conducted by this complex catalyst using Oxone as oxidant under biphasic reaction conditions (CH2Cl2/H2O) and tetra-n-butylammonium bromide as phase transfer agent under air at room temperature.
Copper complexes of the amino acids histidine, arginine and lysine have been introduced into the supercages of zeolite Y and, for the first time, into the large intracrystalline cavities of zeolites EMT and MCM-22. The resulting host/guest compounds are characterized by X-ray powder diffraction, UV/VIS-spectroscopy in the diffuse reflectance mode and by catalytic tests in the liquid-phase oxidation of aromatic alcohols (viz. benzyl alcohol, 2- and 3-methylbenzyl alcohol and 2,5-dimethylbenzyl alcohol) with tertiary-butylhydroperoxide as oxidant. It was observed that intracrystalline copper-amino acid complexes possess remarkable catalytic activity, yielding the corresponding aromatic aldehydes and acids. (orig.)
The effect of complexing agents DTPA and H2C2O4 on the extraction-chemical behavior of Tc, as applied to extractive splitting of U and Pu in the Purex process, was studied. The kinetic relationships of catalytic decomposition of N2H5NO3 under the action of Tc in the presence of these agents were determined. Variation of the ratio of the oxidized and reduced Tc species in the course of this process at various HNO3 concentrations was examined. In the final step of the reaction of N2H5NO3 with Tc in a nitric acid solution, when the reductant content is stabilized, the oxidation of reduced Tc also stops or continues at a considerably lower rate than before stabilization. The presence of DTPA decreases the rate of Tc(IV) oxidation owing to its binding in a complex and decreases the fraction of ...
The possibilities to grow isolated structures of complexoxides by pulsed laser deposition through stencils were investigated. A stencil consisting of a SiN membrane with apertures of several hundred nanometers embedded in a Si chip is placed in front of a heated substrate (up to 750 degrees Celsius). Deposition through these apertures results in resistless, direct patterning by local deposition of complexoxides like ferroelectric Lead Zirconate Titanate. The created isolated structures were analyzed by AFM imaging. Under-deposition, in this work called broadening, is inevitable during stencil deposition and is depending on deposition parameters, especially pressure. Different causes of broadening are mapped and discussed.
To apply the CO{sub 2} absorber at about 1000{sup o}C for integrated coal gasification combined cycle (IGCC) furnace, the reactions of calcium oxide and CO{sub 2} at high temperatures was examined. Calcium carbonate reacts with sodium hydrogen carbonate below 200{sup o}C and forms sodium-calcium complex carbonate. The sodium-calcium complex carbonate melts at 813{sup o}C, and the carbon dioxide absorption and discharge reversible reactions of calcium-oxide takes place via liquid at around 1000{sup o}C. Sintering of calcium oxide at high temperature has been successfully avoided by the addition of sodium.
Americium extraction in different oxidation states in two-phase aqueous system based on polyethylene glycol is investigated. Conditions for quantitative extraction of americium (3) and americium (5) from ammonium sulfate solutions within pH=3-5 interval in the presence of arsenazo 3 are found. Composition of the produced americium complexes with reagent is determined; americium (3) interacts with arsenazo 3 in ammonium sulfate solutions with the formation of MeR and Me_2R composition complexes. Absorption spectrum characteristics of americium (3) and- (5) complexes with arsenazo 3 in ammonium sulfate solutions and extracts based polyethylene glycol aqueous solutions are given. Molar extinction coefficients of americium complexes with arsenazo (3) in these solutions are determined.
Batch interaction experiments were performed under aerobic conditions to characterize the adsorption behavior and valence speciation of CoEDTA complexes (equimolar at 10 -5 mol/L) in a series of Pliocene subsurface sediments containing various amounts of Fe and Mn oxides. The experiments were performed in 0.003 mol/L Ca(ClO 4 ) 2 with a solids concentration of 500 g/L at variable pH (4-9) and at the natural pH of the sediments (pH = 8.3). Three of these subaerial sediments (Ringold 1, 2, 3) contained significant quantities of extractable Fe and Mn, while the fourth (Ringold 4) was virtually devoid of sesquioxide precipitates. Microscopic and mineralogic analyses of the most heavily encrusted material (Ringold 2) showed that the oxides existed as intergrain cements and contained crystalline goethite and rancieite/todorokite. Adsorption on a synthetic analog sorbent (0.6 mass % ferrihydrite-coated sand) over a range in pH ...
Alveolar enlargement, which is characteristic of bronchopulmonary dysplasia, congenital matrix disorders, and cigarette smoke-induced emphysema, is thought to result from enhanced inflammation and ensuing...Full Text Available
Batch interaction experiments were performed under aerobic conditions to characterize the adsorption behavior and valence speciation of CoEDTA complexes (equimolar at 10{sup -5} mol/L) in a series of Pliocene subsurface sediments containing various amounts of Fe and Mn oxides. The experiments were performed in 0.003 mol/L Ca(ClO{sub 4}){sub 2} with a solids concentration of 500 g/L at variable pH (4-9) and at the natural pH of the sediments (pH = 8.3). Three of these subaerial sediments (Ringold 1, 2, 3) contained significant quantities of extractable Fe and Mn, while the fourth (Ringold 4) was virtually devoid of sesquioxide precipates. Microscopic and mineralogic analyses of the most heavily encrusted material (Ringold 2) showed that the oxides existed as intergrain cements and contained crystalline goethite and rancieite/todorokite. Adsorption on a synthetic analog sorbent (0.6 mass% ferrihydrite-coated sand) over a ...
Lebers hereditary optic neuropathy (LHON), the most frequent mitochondrial disorder, is mostly due to three mitochondrial DNA (mtDNA) mutations in respiratory chain complex I subunit genes: 3460/ND1, 11778/ND4 and 14484/ND6. Despite considerable clinical evidences, a genetic modifying role of the mtDNA haplogroup background in the clinical expression of LHON remains experimentally unproven. We investigated the effect of mtDNA haplogroups on the assembly of oxidative phosphorylation (OXPHOS) complexes in transmitochondrial hybrids (cybrids) harboring the three common LHON mutations. The steady-state levels of respiratory chain complexes appeared normal in mutant cybrids. However, an accumulation of low molecular weight subcomplexes suggested a complex I assembly/stability defect, which was ...
The bioenergetic capacity of skeletal muscle in a 17-year-old patient with a severe defect in complex III of the electron transport chain has been examined by 31P NMR measurements of the molar ratio...Full Text Available
Dissolved humic substances (humic and fulvic acids) occur in surface waters and groundwaters in concentrations ranging from less than 1 mg(C)/L to more than 100 mg(C)/L. Humic substances are strong complexing agents for many trace metals in the environment and are also capable of forming stable soluble complexes or chelates with radionuclides. Concentrations of humic materials as low as 1 mg(C)/L can produce a detectable increase in the mobility of some actinide elements by forming soluble complexes that inhibit sorption of the radionuclides onto rock materials. The stability of trace metal- or radionuclide-organic complexes is commonly measured by an empirically determined conditional stability constant (K'), which is based on the ratio of complexed metal (radionuclide) in solution to the product concentration of uncomplexed metal and humic complexant. ...
A predictive reactivity of Cp_2An(IV)Me_2 (with An = uranium [U], neptunium [Np] and plutonium [Pu]) with pyridine N-oxide has been studied at the theoretical level. The predictive reaction, which consists in the formation of a formaldehyde complex, begins after the initial formation of a cyclo-metalated complex produced by a C-H activation of the pyridine N-oxide. A difference of reactivity between U/Pu and Np has been observed and has been attributed to the presence of a more covalent bond between Np and the carbene group in the transition state of formation of a transient carbene intermediate. (authors)
The effect of a series of complexing and reducing agents on the extraction-chemical behavior of technetium as applied to extraction splitting of uranium and plutonium in the Purex process was examined. Kinetic parameters of the catalytic decomposition of N2H5NO3 under the action of Tc in the presence of these agents were evaluated. Variation of the ratio of the oxidized and reduced Tc species in the course of the process and in the hydrazine-free systems was determined. Reagents preventing oxidation of the reduced technetium and decomposition of N2H5NO3 in nitric acid solutions (acetohydroxamic acid, hydroxylamine, ascorbic acid, etc.), inhibiting the reduction of Tc with hydrazine nitrate (H2O2, HN3, etc.), and known as complexing agents toward quadrivalent actinides but indifferent to Tc...
Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for ...
Pulse reactor experiments were conducted on the reactions of unlabeled or deuterium- or oxygen-18-labeled allyl alcohols over molybdenum trioxide and various bismuth molybdates in the absence or presence of oxygen and ammonia. The allyl alcohol apparently adsorbed on oxidation sites to form acrolein via allyl molybdates, and on Broensted acid sites to form diallyl ether via an allyl carbonium ion. The bismuth enhanced ..cap alpha..-hydrogen abstraction, which was the rate-determining step in the oxidation. The product distributions provided evidence that the selective oxidation of propylene to acrolein proceeds via a m-allyl molybdate which collapses to an O o-allyl molybdate prior to the second hydrogen abstraction, and that the analogous N o-complex in ammoxidation undergoes two hydrogen abstractions to form acrylonitrile. Detailed reaction schemes are developed.
Abstract Despite the fact that oxidation is the second most frequent degradation pathway for pharmaceuticals, means of evaluating the oxidative stability of pharmaceutical solids, especially effective stress testing, are still lacking. This paper describes a novel experimental method for peroxide-mediated oxidative stress testing on pharmaceutical solids. The method utilizes urea-hydrogen peroxide, a molecular complex that undergoes solid-state decomposition and releases hydrogen peroxide vapor at elevated temperatures (e.g., 30C), as a source of peroxide. The experimental setting for this method is simple, convenient, and can be operated routinely in most laboratories. The fundamental parameter of the system, that is, hydrogen peroxide vapor pressure, was determined using a modified spect...
Formation of the complex of the univalent astatine cation with nitrilotriacetic acid (AtL)[sup 2-] and its stability constant (lgK[sub 1]=8.97(4), 25degC, [mu]=0.1) have been found experimentally for the first time. The complex is stable in perchlorate solutions in presence of 5 . 10[sup -3] mol . l[sup -1] of the oxidizer Na[sub 2]S[sub 2]O[sub 8] in the interval 4[<=]pH[<=]8.5. The complex is supposed to be destroyed in weak alkaline solutions by reduction of astatine to astatide. The deprotonation constant of hypoastatic acid pK[sub dp]=5.23(9) was found to be lower than determined previously. The investigation was carried out by the method of ion electrophoresis in free electrolyte solutions. (orig.).
Formation of the complex of the univalent astatine cation with nitrilotriacetic acid (AtL)"2"- and its stability constant (lgK_1=8.97(4), 25degC, #mu#=0.1) have been found experimentally for the first time. The complex is stable in perchlorate solutions in presence of 5 . 10"-"3 mol . l"-"1 of the oxidizer Na_2S_2O_8 in the interval 4#<=#pH#<=#8.5. The complex is supposed to be destroyed in weak alkaline solutions by reduction of astatine to astatide. The deprotonation constant of hypoastatic acid pK_d_p=5.23(9) was found to be lower than determined previously. The investigation was carried out by the method of ion electrophoresis in free electrolyte solutions. (orig.).
Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. ...
The oxidative dehydrogenation (ODH) of light alkanes is an alternative way for the production of olefins. A wide variety of catalytic systems has been investigated. Vanadium oxide based catalysts were described in the literature as effective catalysts for the ODH of propane. The catalytic activity and selectivity depend on the kind of support material, the kind of dopants and the formation of complex metal oxide phases. In recent papers it was claimed that both orthovanadate and/or pyrovanadate species are selective for the ODH of propane. Niobia based materials were investigated as catalysts for acidic and selective oxidation type reactions. In the ODH of propane niobia exhibited a high selectivity to propene but the conversion of propane was low. V{sub 2}O{sub 5}-Nb{sub 2}O{sub 5} catalysts proved to be catalytically active and selective and showed no formation of oxygenates. In ...
The reaction of the chelating ligands (obtained by the condensation of 2-hydroxy-1-naphthaldehyde with various primary amines) with [RuHCl(CO)(EPh3)2(B)] (where E=P; B=PPh3, py or pip: E=As; B=AsPh3) in benzene afforded new stable ruthenium(II) carbonyl complexes of the general formula [Ru(Cl)(CO)(EPh3)(B)(L)] (L=anion of bidentate Schiff bases). The structure of the new complexes was investigated using elemental analyses, spectral (FT-IR, UV-vis and 1H NMR) and electrochemical studies and is found to be octahedral. All the metal complexes exhibit characteristic MLCT absorption and luminescence bands in the visible region. The luminescence efficiency of the ruthenium(II) complexes was explained based on the ligand environment around the metal ion. These complexes catalyze oxidation of prim...
Oxidative degradation of methylene blue (MB) by Co^2^+-HCO3^- system with H2O2 in aqueous solution was studied. Nearly complete decolorization of the dye was obtained in less than 50min in diluted NaHCO3 solution (25mM) in the presence of only 20mM Co^2^+ ions. Meanwhile, the conjugated structure and phenyl rings of the MB molecule were destroyed or even broken down into small organic acids and inorganic ions, as indicated by FT-IR spectra and ion-chromatography. Photoluminescence probing and radical scavenging technologies suggested that the reaction of MB degradation in this system mainly involved the generation and participation of hydroxyl radicals. Furthermore, by cyclovoltammetric measurements, the in situ formed different complexes between Co^2^+ and HCO3^- were observed at differen...
During solvent extraction of At"-, [At(H_2O)_2]"+, AtCl, AtCl_2"- as well as of astatine compounds with higher oxidation states like AtO_n"-, the astatine species are changed into astatine of the oxidation state zero at the phase boundary independent on the organic solvent used. At(O) probably reacts with components of the organic phase or with decomposition products formed by chemical reactions or by radiolysis. The extraction coefficients of the astatine species depend on the experimental conditions applied, the redox potential, and on complex forming reactions or associations, resp., occuring in the aqueous phase. (author).
A review is given of the state of knowledge of the chemistry of astatine with the oxidation number +1. According to the position in the periodic system, astatine has metalloidal properties. The existence of a singly-charged cation in acid solution and the complex formation reactions with halide ions (Cl"-, Br"-, and I"-), with pseudohalide ions (SCN"-, CN"-, C(CN)_3"-, and N_3"-), and with thioureas and their derivatives underline the metalloidal character of At(I). Optimal preparation conditions, chemical composition of astatine compounds, existence and stability regions of At(I) complexes, and stability constants have been investigated by means of electromigration in free electrolyte solutions.
The nature and properties of inorganic /sup 211/At-species formed in aqueous solutions under alkaline, neutral, acidic and oxidative conditions are studied through extraction of At with a variety of organic solvents, followed by the determination of the chromatographic, re-extraction and interaction behaviour of the extracted activity. It is concluded from the Rsub(f) values (on SiO/sub 2/) and the different affinities for a large amount of additives, that the extracted activity - formerly denoted as At-zero - exists of AtX compounds that may form AtXLsub(u) complexes, depending on the kind of solvent (L) used.
The nature and properties of inorganic "2"1"1At-species formed in aqueous solutions under alkaline, neutral, acidic and oxidative conditions are studied through extraction of At with a variety of organic solvents, followed by the determination of the chromatographic, re-extraction and interaction behaviour of the extracted activity. It is concluded from the Rsub(f) values (on SiO_2) and the different affinities for a large amount fo additives, that the extracted activity - formerly denoted as At-zero - exists of AtX compounds that may form AtXLsub(u) complexes, depending on the kind of solvent (L) used. (orig.).
The state of prooxidant-antioxidant homeostasis in Guinea pigs exposed to whole-body fractionated X-irradiation (5 fractions of 0.2 Gy at a 24 hr interval, up to total dose of 1.0 Gy, at a dose rate of 0.425 R/min) and a possibility of its disturbance correction with the complex of vitamins C, E and P was studied. Accumulation of primary and secondary lipid peroxidation products, decrease of the ascorbic acid content, increase of the content of its oxidized forms (dehydroascorbic acid and diketogulonic acid) in radiosensitive and radioresistant organs were found. Antioxidant complex administration reduced the disturbances of prooxidant-antioxidant homeostasis, but did not provide complete normalization.
The proposed active sites on the catalyst surface in heterogeneous propylene ammoxidation have been successfully modelled by structurally characterized pinacolato W(VI) tert-butylimido complexes. These compounds exist as an equilibrating mixture of amine-bis(imido) and imido-bis(amido) complexes, the position of this equilibrium is dependent on the electronic nature of the glycolate ligand. Both of the C-N bond-forming reactions proposed in recent studies by Grasselli et al. (1) have been reproduced using discrete Group VI d{sup 0} organoimido complexes under mild conditions suitable for detailed mechanistic studies. These reactions are: (1) oxidative trapping of radicals at molybdenum imido sites, and (2) migration of the allyl group from oxygen to an imido nitrogen atom.
Spectrophotometry was used to study the conditions under which three-component complexes are formed of rare-earth elements (REE) with aminopolycarboxylic complexes and #beta#-diketones; the molar extinction coefficients of the above REE complexes were also found. A procedure is suggested for determining REE in chromatographic eluates with lower boundary of the contents determined being at 0.6-1.5 #mu#g/ml (Pr, Nd, Ho and Er) and 5-7 #mu#g/ml (Sm and Tm) with account for oxides. Luminescent techniques were also suggested for determining terbium in the presence of EDTA and terbium in an eluate containing EDTA and oxyethyl ethylene diamine triacetic acid, both acids being characterized by a relative standard deviation equal to 0.015-0.03.
Electrodeposition of semiconducting iron oxide (Fe_2O_3) thin film was carried out from an alkaline sulphate bath. A 0.1 M ferrous sulphate (FeSO_4#centre dot#7H_2O) was complexed with 0.1 M citric acid. By addition of 1 N NaOH, pH of the solution was made alkaline (pH=9) and deposition of iron oxide (Fe_2O_3) thin films was carried out potentiostatically at room temperature (300 K). From cyclic voltametry (CV), electrochemical studies were carried out for deposition of iron oxide thin films. The XRD studies reveal that Fe_2O_3 with epsilon (#epsilon#) phase having monoclinic crystal structure is formed. By observing scanning electron microscope (SEM), it is seen that iron oxide films were homogeneous, uniform and well covered to surface of the substrate. Grain size was found to be in nanometers range from XRD analysis. The optical band gap of Fe_2O_3 thin film was estimated to be ...
Within the framework of a study on the chemical wear behaviour of sialon ceramics a range of compositions were prepared in which the alumina content was varied from 6 to 77 weight percent. The materials were hot-pressed from alumina and silicon nitride powders to a density of at least 97%. The structure and compositions of the phases occurring in these samples i.e. the O' phase, #beta#'-sialon solid solution and especially the X-phase were thoroughly characterized with respect to structure and composition using electron microprobe and transmission electron microscopy techniques. These results will be discussed in the light of earlier phase diagram studies. Some basic properties such as E-modulus and toughness were measured and related to microstructural features. E-modulus as well as toughness are at a minimum for materials with a high content of the X-phase. Oxidation of the materials was studied at 1300 deg C and 1450 deg C using weight gain measurements and ...
Reaction between [V^I^VO(acac)2] and the ONN donor Schiff base Hpydx-aepy (I) (Hpydx-aepy=Schiff base obtained by the condensation of pyridoxal and 2-aminoethylpyridine) resulted in the formation of a complex [V^I^VO(acac)(pydx-aepy)] (1). Addition of aqueous 30% H2O2 to 1 yields the poor stable oxidoperoxidovanadium(V) complex [V^VO(O2)(pydx-aepy)] (2). Its formation has also been demonstrated in solution by treating 1 with H2O2 in methanol. Reaction of vanadium exchanged zeolite-Y with I in methanol followed by aerial oxidation gave zeolite-Y encapsulated dioxidovanadium(V) complex, abbreviated as [V^VO2(pydx-aepy)]-Y (4). The crystal and molecular structure of 1 has been determined, confirming the ONN binding mode of the ligand. The encapsulated complex [V^VO2(pydx-aepy)]-Y (4) catalyse...
A series of (diamine)isopropylidenmalonatoplatinum(II) complexes and the oxidation products, (diamine)Pt(OOC){sub 2}C=C(CH{sub 3}){sub 2}(X){sub 2}, (diamine=ethylenediamine(en), 1,2-diaminopropan(dap), N-methylethylenediamine(men); X=OH, OCOCH{sub 3}, OCOCF{sub 3}), have been prepared, and their interaction with guanosine-5'-monophosphate (5'-GMP) have been examined by means of {sup 1}H NMR spectroscopy. The present platinum(II) complexes have shown to interact with 5'-GMP through N7 coordination in two consecutive steps in a similar way as with cisplatin, but no interaction between the present platinum(IV) complexes and 5'-GMP was observed. However, in the presence of ascorbic acid, the platinum(IV) complexes have been found to interest with 5'-GMP with the reation rate depending on their reduction rate.
We used fast absorbance spectroscopy to investigate in vivo binding dynamics and electron transfer between plastocyanin (pc) and photosystem I (PSI), and cytochrome (cyt) f...Full Text Available
Drilling fluid additives are prepared by oxidation of sulfonated lignin-containing materials with manganese dioxide under highly acidic conditions to make manganese lignosulfonates. Additional improvements in the rheological properties of the additives may be obtained by complexing the manganese lignosulfonate so obtained with a heavy metal cation (preferably iron or copper), by, for example, addition of ferrous sulfate or ferric sulfate to the manganese lignosulfonate. These products show the requisite combination of rheological properties for a satisfactory drilling fluid additive or conditioner.
The concept of nanocrystal conversion chemistry, which involves the use of pre-formed nanoparticles as templates for chemical transformation into derivative solids, has emerged as a powerful approach for designing the synthesis of complex nanocrystalline solids. The general strategy exploits established synthetic capabilities in simple nanocrystal systems and uses these nanocrystals as templates that help to define the composition, crystal structure, and morphology of product nanocrystals. This article highlights key examples of 'conversion chemistry' approaches to the synthesis of nanocrystalline solids using a variety of techniques, including galvanic replacement, diffusion, oxidation, and ion exchange. The discussion is organized according to classes of solids, highlighting the diverse target systems that are accessible using similar chemical concepts: metals, oxides, chalcogenides, phosphides, alloys, intermetallic ...
The 1H NMR, electronic absorption, and luminescence spectra, as well as voltammograms of the reduction and oxidation of the complexes [Pd(C?N)(N?N)]ClO4 and [Pd(C?N)(?-OOCCH3)]2 [where (C?N)? is deprotonated 2-phenyl-4,5-dihydro-1,3-oxazole, and N?N is ethylenediamine or 2,2?-bipyridine (bpy)] were compared. Magnetic nonequivalence of protons in the dihydrooxazole ring and upfield shift of the corresponding signals were observed as a result of anisotropic effect of the ring current in palladated phenyl substituents in the [Pd(C?N)(?-OOCCH3)]2 complex having a C 2 symmetry. One-electron reduction wave of [Pd(C?N)bpy]+ was assigned to ligand-centered electron transfer to the ?* orbital of 2,2?-bipyridine, and two oxidation waves of [Pd(C?N)(?-OOCCH3)]2 were attributed to successive one-elect...
Anionic complexes of transition metals were stabilized in aqueous solutions containing high concentrations of various short-chain quaternary ammonium salts. Compounds with longer paraffin chains were effective in much less concentrated solution. Complex ions were detected spectrophotometrically. FeCl/sub 4//sup -/, which is usually formed in concentrated HCl, was the predominant Fe(III) complex in 30 m choline chloride containing only 0.12 M HCl. A yellow transitory Tc(VII) chloro-addition intermediate, formed in the reduction of TcO/sub 4//sup -/ by concentrated HCl, was stabilized when the solution also contained 25 m choline chloride. Its spectrum, as well as the isolation of an already known Tc(VII) bipyridyl complex, is reported. Concentrated organic electrolytes also stabilized Tc(V) oxide halides against disproportionation and Tc(IV) hexahalides against hydrolysis. ...
The effects of the structure of a carboxylic acid on the processes of oxidation and reduction of iron ions in irradiated aqueous solutions were directly observed during irradiation. The solutions contained the mono- or dicarboxylic acid, H/sub 2/SO/sub 4/, Fe(NH/sub 4/)/sub 2/(SO/sub 4/)/sub 2/ and O/sub 2/. Th e ferrous oxidation was rather independent of the acid and its concentration, but the reduction of ferric was possible in the presence of formic, oxalic, or valeric acid only. The radical formed from the valeric acid acts similar to those formed from hydrocarbons. The G-values of oxidation and reduction of the iron ions were established. The molar extinction coefficients for oxalic and malonic complexes of ferric ions were determined. (auth)
The kinetics of the oxidative addition of CH/sub 3/I to platinum(II) complexes in aqueous solutions of K/sub 2/PtCl/sub 4/ and KPtCl/sub 3/(C/sub 2/H/sub 4/) have been studied by PMR and GLC. The second-order rate constants for the PtCl/sub 3/(H/sub 2/O)/sup -/ and PtCl/sub 4//sup 2 -/ particles are equal to 400 exp(-2.7 x 10/sup 3//T) and 3.18 x 10/sup 10/ exp(-9.2 x 10/sup 3//T) mole/sup -1/ x liter x sec/sup -1/, respectively. The introduction of a ..pi..-acceptor ligand, viz. ethylene, into the coordination sphere of platinum(II) results in a sharp drop in the rate, probably due to a decrease in the electron density on the platinum atom. According to the PMR data, the product of the oxidative addition of CH/sub 3/I to Zeise's salt is a methyl complex of platinum(IV), is identical to the complex obtained by reacting methyl iodide with K/sub 2/PtCL/sub 4/, and does not ...
The liquid-phase synthesis of metal oxide nanoparticles in organic solvents under exclusion of water is nowadays a well-established alternative to aqueous sol-gel chemistry. In this article, we highlight some of the advantages of these routes based on selected examples. The first part reviews some recent developments in the synthesis of ternary metal oxide nanoparticles by surfactant-free nonaqueous sol-gel routes, followed by the discussion of the morphology-controlled synthesis of lanthanum hydroxide nanoparticles, and the presentation of structural peculiarities of manganese oxide nanoparticles with an ordered Mn vacancy superstructure. These examples show that nonaqueous systems, on the one hand, allow the preparation of compositionally complexoxides, and, on the other hand, make use of the organic components (initially present or formed in situ) in the reaction mixture to ...
CuO/bentonite and CuO-BHA nanocomposites were studied as oxygen carriers in chemical-looping combustion (CLC) of simulated synthesis gas. Global reaction rates of reduction and oxidation, as the function of reaction conversion, were calculated from 10-cycle oxidation/reduction tests utilizing thermogravimetric analysis at atmospheric pressure between 700 and 900{degree}C. It was found that the reduction reactions are always faster than oxidation reactions; reaction temperature and particle size do not significantly affect the reaction performance of CuO/bentonite. Multicycle CLC tests conducted in a high-pressure flow reactor showed stable reactivity for production of CO{sub 2} from fuel gas at 800 and 900{degree}C and full consumption of hydrogen during the reaction. Results of the tapered element oscillating microbalance showed a negative effect of pressure on the global rates of reduction-oxidation ...
Total (elastic+inelastic) cross sections for electron impact on FeO, Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} have been calculated in the energy range 20-5000 eV by employing the additivity rule which expresses the total cross section of a molecule as an incoherent sum over the total cross sections of the constituent atoms of the molecule. The electron-atom cross sections have been obtained by a complex optical potential method through partial-wave analysis. The total cross sections for all the oxides of iron exhibit a maximum around 30 eV. The inelastic cross sections are upper bounds to the corresponding ionisation cross sections. Bethe parameters for inelastic cross sections are given. ((orig.))
The evaluation of the bactericidal effect of different silver-containing materials where silver is available as Ag^+ (silver nitrate and different silver-exchanged zeolites), as metallic Ag^0 (commercial silver nanoparticles) or as oxide (silver (I) oxide) was carried out in order to elucidate the importance of the bioavailability of silver (i.e., as free ions, metallic particles, combination of them, clusters, complexes, partially soluble or insoluble salts, etc.) on its bactericidal action. For the different materials tested, their bactericidal effect is ordered in the following sequence: AgNO"3>Ag-ZSM-5>Ag"2O>commercial silver-exchanged zeolite (granular)>commercial silver-exchanged zeolite (pellets)>Ag nanoparticles. In general, as the content of bioavailable ionic silver increases, th...
Polymeric coated ferromagnetic carriers with an absorbed layer of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) diluted by tributyl phosphate (TBP) are being evaluated for application in the separation and the recovery of low concentrations of americium, plutonium, and uranium from nuclear waste solutions. Due to their chemical nature, these extractants selectively complex americium and plutonium contaminants onto the particles and the complexed particles can be recovered from the solution using a magnet. Physical and chemical characterization of the extractant-absorbed particles were performed by gamma and liquid scintillation counting, scanning electron microscopic (SEM) micrograph, and other physical measurements. Plutonium, americium, and uranium separations have been performed at various HNO{sub 3} and HCl concentrations. Parameters were studied to determine the limitations and capacity of the ...
A study has been made of the colour reaction involved in the interaction or rare-earth elements with the reagent orthanyl K, the optimum conditions for the reaction being: pH=4.0-4.5 and lambda=660-670 nm. The ratio of components in the complex is Me:R=1:2. Consideration of the relative optical density values of the complex solutions as a function of the serial number of the rare-earth elements made it possible to recommend orthanyl K as a selective reagent for determining La, Ce, Pr and Nb in a mixture of Tu, Yb, Lu and Y oxides. The molar extinction coefficients, the sensitivity of the reaction and the concentration limits where Beer's law applies were calculated. Lanthanum was determined in a binary mixture with thulium and yttrium. (author).
A rapid combustion unit (Baird and Tatlock) incorporating a combustion chamber provided with baffle plates for complete combustion of the sample without the use of a catalyst has been assembled in a glove box for the determination of carbon and hydrogen in actinide complexes. The unit has been modified employing a movable electric furnace and a proportional temperature controller, for decomposition of the sample at desired heating rates. The set-up was standardised employing various reference materials such as benzoic acid, acetanilide, sulphanilamide and 1-chloro 2:4 dinitrobenzene and the standard deviation in the measurements evaluated. It has also been used successfully for the determination of carbon in uranium carbide and carbon and hydrogen in some uranyl-#beta#-diketone-amine N-oxidecomplexes and in plutonium(IV) oxalate. (auth.).
A rapid combustion unit (Baird and Tatlock) incorporating a combustion chamber provided with baffle plates for complete combustion of the sample without the use of a catalyst has been assembled in a glove box for the determination of carbon and hydrogen in actinide complexes. The unit has been modified employing a movable electric furnace and a proportional temperature controller, for decomposition of the sample at desired heating rates. The set-up was standardised employing various reference materials such as benzoic acid, acetanilide, sulphanilamide and 1-chloro 2:4 dinitrobenzene and the standard deviation in the measurements evaluated. It has also been used successfully for the determination of carbon in uranium carbide and carbon and hydrogen in some uranyl-#beta#-diketone-amine N-oxidecomplexes and in plutonium(IV) oxalate. (auth.).
The kinetics of oxidation of uranium (IV) monofluoride complex by nitrous acid in nitric acid solution have been studied. The experiments were carried out at constant ionic strength of 2M (HNO_3 and NaNO_3) and temperature in the range of 18-47 deg C. The rate of reaction was determined spectrophotometrically at a wavelength of 621 nm, at which the molar extinction coefficients of UF"3"+ and UF_2"2"+ are the same. It was shown that reaction orders for [HNO_2] and [HNO_3] are equal to 0.12 and 0.39, respectively. The values of activation parameters #DELTA#H"#not =# and #DELTA#S"#not =# are determined to be 83 kJ mol"-"1 and 75 J (mol.K)"-"1, respectively. The rate order of the reaction studied has a weak direct depedence on [H"+] in contrary to the strong and reverse dependence in the absence of fluoride ions. In conclusion, fluoride ions may strongly stabilize the U(IV) in nitric acid solutions. (author) 4 refs.; 3 figs.; 2 tabs.
The development of detailed chemical kinetic reaction mechanisms for analysis of autoignition and knocking of hydrocarbon fuels is described. In particular, kinetic processes of concern for the oxidation of complex hydrocarbon fuel molecules are emphasized. The wide ranges of temperature and pressure which are encountered by end gases in automobile engine combustion chambers result in extreme demands on reaction mechanisms which are intended to describe knocking conditions and predict rates of combustion and ignition. The reactions and chemical species which are most important in each temperature and pressure regime are discussed, and the validation of these reaction mechanisms through comparison with idealized experimental results is described. 53 refs., 8 figs., 5 tabs.
The radiation degradation behavior of three commercial polyvinyl chloride (PVC) materials has been investigated. All three exhibit an interesting reversal in the trend of the tensile strength part way through the aging experiment: the tensile strength first drops, then rises. The early drop is associated with oxidative scission; the rise is associated with crosslinking and is preceded by the material reaching the gel point. It was also found that the tensile elongation tended to level out in advanced stages of aging with the levelling-out values dependent on the dose rate. These phenomena pose complications for the design of accelerated aging tests. (author).
The radiation degradation behavior of three commercial polyvinyl chloride (PVC) materials has been investigated. All three exhibit an interesting reversal in the trend of the tensile strength part way through the aging experiment: the tensile strength first drops, then rises. The early drop is associated with oxidative scission; the rise is associated with crosslinking and is preceded by the material reaching the gel point. It was also found that the tensile elongation tended to level out in advanced stages of aging with the leveling-out values dependent on the dose rate. These phenomena pose complications for the design of accelerated aging tests.
The aim of this work is to understand the reasons for the selectivity shown in the complexation by unsaturated heteropolyanions (HPA) of actinides (An) which are oxidized to the number +IV. Different studies have been carried out, both in solution and in solid state, on P_2W_1_7O_6_1"1"0"- and its complexes with Zn"2"+, UO_2"2"+, Ce"4"+, Th"4"+ and U"4"+ to characterize the nature of the complexation site offered to the cation. Among the actinides(IV), the U"4"+ ion has been selected due to its singular spectroscopic and magnetic properties. An initial series of studies, in solution, using NMR"3"1P has thus enabled us to characterize these complexes and to compare them to those formed with the complexing agent PW_1_1O_3_9"8"-. This body of data allows to identify an identical complexation site for both ligands. An analysis of the NMR"3"1P ...
The quantitative determination of oxide concentration by laser-induced breakdown spectroscopy is relevant in various fields of applications (e.g.: analysis of ores, concrete, slag). Calibration free laser-induced breakdown spectroscopy and the multivariate calibration are among the methods employed for quantitative concentration analysis of complex materials. We measured the intensity of neutral and ionized atomic emission lines of oxide materials by laser-induced breakdown spectroscopy and we modified the calibration free laser-induced breakdown spectroscopy method to increase the accuracy. The concentration of oxides was obtained by using stoichiometric relations. Sample materials were prepared from oxide powder (Fe{sub 2}O{sub 3}, MgO, CaO) by mixing and pressing. The concentration was 9.8-33.3 wt.% Fe{sub 2}O{sub 3}, 7.6-33.3 wt.% MgO and 33.3-81.2 wt.% CaO for different ...
The vast majority of fundamental studies of metal oxide selective oxidation catalysts have been performed with single phase systems. These investigations established the basic tenents of the redox mechanism of selective oxidation and ammoxidation catalysis. By comparison, structural and kinetic investigations of multiphase oxide catalysts are less numerous because of the inherent difficulties in understanding the relative contributions of separate phases to the catalytic behavior of the composite catalyst. Some attempts have been made in the past to understand the complex chemistry of multiphase catalysts and additional important insights have been realized more recently. However, a clear understanding of the most significant catalytic interactions between individual phases of a multiphase multicomponent redox catalyst is still lacking. In an effort to provide an understanding and a ...
In view of the effect of the acidity on the oxidation potentials of nitrous, arsenous, and arsenic acids, one should expect a complex relationship between the rate of arsenic (III) to arsenic (V) and the pH of the solution. They studied the kinetics of the reaction 2AsO/sub 2//sup -/ + O/sub 2/ ..-->.. 2AsO/sub 3//sup -/ as functions of concentrations (partial pressure) of all the components of the system NaAsO/sub 2/-HCl(HClO/sub 4/)-NaNO/sub 2/-KI-H/sub 2/O-O/sub 2/ and temperature. The study of the kinetics of arsenic(III) oxidation to arsenic(V) with oxygen in the presence of sodium nitrite and iodide ions showed that the reaction rate passes through a maximum at an acid content of 1.2-2.5 M and rises in proportion to the second exponent of the sodium nitrite concentration and to the first exponent of the iodide ion concentrations and partial oxygen pressure. A fall in the temperature facilitates intensification of ...
The metal dependence of mesoporous activated carbons with various metal acetylacetonate (acac) particles prepared from Morwell coal was studied. In experiment, the mixture of Morwell coal and acac metal complexes were dissipated into tetrahydrofuran, and after agitation in Ar atmosphere, the solvent was removed by vacuum distillation. Coal specimens with Fe(acac)3, Ni(acac)2 and Co(acac)2 as acac complexes were activated by exchanging flow gas with water vapor after heat treatment in N2 gas flow at 900{degree}C. The pore sizes of the specimens were obtained from N2 adsorption isotherms by BET method and BJH method. Conditions of pores and metals in the specimens were examined by XRD measurement and TEM observation. The relation between the above conditions and pore characteristics obtained from adsorption experiment was also examined. As a result, the difference in mesopore ratio between the specimens and blank specimens was larger in the order ...
A detailed kinetic study of the epoxidation of 1-octene with hydrogen peroxide catalyzed by Pt(II) complexes is reported. The two systems analyzed were (diphoe)Pt(CF/sub 3/)(OH)/1-octene/H/sub 2/O/sub 2//THF and ((diphoe)Pt(CF/sub 3/)(CH/sub 2/Cl/sub 2/))BF/sub 4//1-octene/H/sub 2/O/sub 2//H/sub 2/O/CH/sub 2/Cl/sub 2/. Rate data were determined with GLC from epoxide formed vs time plots. Evidence for many of the organometallic intermediates and the individual steps involved was gained from IR studies, /sup 19/F NMR studies, and especially designed experiments including studies of the acidity effect. In both cases the kinetic analysis suggests a mechanism in which the actual oxidant is a PtOOH species that interacts with a Pt-olefin complex in the oxygen-transfer step (second-order dependence on platinum). 29 references, 12 figures, 3 tables.
Bis(diphenylphosphino)phenylamine can be selectivity oxidized by S or Se in toluene or hexane solvents to the monooxidized thioyl or selenoyl products Ph[sub 2]PN(PH)PPh[sub 2]=E, (E = S, Se). These compounds act as bidentate chelate ligands toward metal complexes forming (CO)[sub 4]M(LL) (M = Mo, W), CO(Cl)Rh(LL), and Cl[sub 2]M(LL), (M = Pt, Pd) where (LL) is the thioyl or selenoyl derivative of the aminobis(phosphine). IR and NMR data are given for all complexes. The carbonyl infrared stretching frequencies show that the chelates form with the phosphine cis to any CO which is present. The [sup 31]P NMR of all complexes of two doublets except for the Rh complexes wherein the Rh spin also couples to phosphorous to produce two doublets of doublets. The [sup 2]J[sub PP] values range from 56 to 112 Hz. [sup 1]J[sub PSe] coupling provide valuable assistance for the assignment of the ...
Proposals for use of Alloy 800 as a H.T.R. boiler material have prompted studies of its creep and high temperature fatigue properties in impure helium with comparative tests in air. In impure helium, as expected in a H.T.R., reactions of potential importance are selective oxidation (of chromium, aluminium and titanium) and possibly carburisation from carbon monoxide or methane. In air, general oxidation will occur, possibly accompanied by nitridation. The effects of these reactions will depend on specimen geometry and the nature of the deformation. Two important possibilities are: (i) that environment affects the structure and properties of a surface zone of material undegoing uniform deformation (this may modify creep rate and crack nucleation); and (ii) that environment affects behaviour of a small region (e.g. at the root of a notch or ahead of a crack) in a specimen undergoing non-uniform deformation (this will modify crack growth and hence ...
There is presently considerable interest in wear resistant coatings produced using closed field unbalanced magnetron sputtering technology. For example, layered films of diamond-like carbon (DLC) with tungsten or titanium additions have been widely reported. The benefit is that the mechanical properties are enhanced (e.g. giving greater toughness); also it is possible to control the stress state and enhance adhesion. Here we report the further development of this concept by the addition of TiN, TiCN and TiC layers in DLC-based composites, utilizing an additional source of electrons in the vicinity of substrate to enhance ionisation of the plasma and increase coating density. Composite coatings of ceramics TiN, TiC{sub x}N{sub y}, TiC, CrN, TiCrN, TiCrCN, TiCrC, metal doped Ti{sub x%}-DLC and their combinations were deposited on 316 stainless steel substrates. The mass flow of reactive gases into the chamber was controlled using plasma optical ...
This dissertation reports on the application of numerical optimization techniques as applied to fuel cell simulation and design. Due to the "multi-physics" inherent in a fuel cell, which results in a highly coupled and non-linear behavior, an experimental program to analyze and improve the performance of fuel cells is extremely difficult. This program applies new optimization techniques with computational methods from the field of aerospace engineering to the fuel cell design problem. After an overview of fuel cell history, importance, and classification, a mathematical model of solid oxide fuel cells (SOFC) is presented. The governing equations are discretized and solved with computational fluid dynamics (CFD) techniques including unstructured meshes, non-linear solution methods, numerical derivatives with complex variables, and sensitivity analysis with adjoint methods. Following the validation of the fuel cell model in 2-D and 3-D, the ...
On-board reforming of liquid fuels to hydrogen for use in proton exchange membrane (PEM) fuel cell electric vehicles (FCEVs) has been the subject of numerous investigations. In many respects, liquid fuels represent a more attractive method of carrying hydrogen than compressed hydrogen itself, promising greater vehicle range, shorter refilling times, increased safety, and perhaps most importantly, utilization of the current fuel distribution infrastructure. The drawbacks of on-board reformers include their inherent complexity [for example a POX reactor includes: a fuel vaporizer, a reformer, water-gas shift reactors, a preferential oxidation (PROX) unit for CO cleanup, heat exchangers for thermal integration, sensors and controls, etc.], weight, and expense relative to compressed H{sub 2}, as well as degraded fuel cell performance due to the presence of inert gases and impurities in the reformate. Partial oxidation (POX) of ...
A strategic partnership was formed among the American Foundrymen`s Society and the Federal government to develop and transfer the technology needed by the US foundry industry to: increase energy efficiency of cupola melting; improve recovery of carbon, silicon, and manganese through reduced oxidation losses; and improve productivity due to more uniform and predictable iron compositions. An effective mathematical model of the cupola offers a solution to the complex and interactive chemical and heat transfer processes to melt cast iron. The transient changes in charge size, charge composition, blast rate, and coke rate are used to optimize operation to improve melting rates, minimize oxidation losses of valuable alloying elements (C, Si, and Mn), and maintain iron composition. Despite these challenges, the cupola produces iron at a lower cost, and have better environmental controls than other melting process with 70% of ...
The French strategy of high level radioactive aqueous waste management is an incorporation in glassy fission products containers. Therefore, nitric acid soluble organic reagents needed for minor actinides and lanthanides selective separation from fission product solutions have to be sufficiently removed to reach carbon concentrations compatible with calcinator working. Thus, the ability of reagents to be oxidized under concentration conditions with or without denitration becomes a criteria of selection and have been studied. Further, if not working, other operations like hot hydrogen peroxide oxidation, catalyzed or not, are investigated. Reagents involved in this work are mainly complexing products (N-(2-Hydroxyethyl) Ethylene-diamine-tri-acetic Acid), pH keeping reagents (carboxylic acids like citric, glycolic, tartaric and lactic acid) and alkaline species (Tetramethylammonium hydroxide). Behaviour of acetic acid, which ...
To reduce the volume of radioactive wastes after evaporation, activity carriers can be separated from the inactive salt load. Boric acid separation from PWR concentrates was considered a preliminary stage for nuclide precipitation. In connection with the precipitation process, the reaction conditions for boric acid separation were determined by bench-scale experiments. After evaluating the known purification processes, crystallization was suggested as a practicable method. After inactive bench-scale experiments, mixed crystal formation with iron hexacyanoferrate for Cs removal was chosen. The disturbing effect of the complexing agents was neutralized by a pre-dose of iron-III-salts. By specifying the precipitation conditions, for Cs-134 an activity separation from 3,0 E + 06 Bg/l to 1,9 E + 02 Bg/l, and for Cs-137 from 5,9 E + 06 Bg/l to 1,2 E + 02 Bg/l was achieved. Accordingly, the decontamination factor for Cs-134 was 16000, and for Cs-137 48000. For the ...
The ability to feed on vertebrate blood has evolved many times in various arthropod clades. Each time this trait evolves, novel solutions to the problem posed by vertebrate hemostasis are generated. Consequently, saliva of blood-feeding arthropods has proven to be a rich source of antihemostatic molecules. Vasodilators include nitrophorins (nitric oxide storage and transport heme proteins), a variety of peptides that mimic endogenous vasodilatory neuropeptides, and proteins that catabolize or sequester endogenous vasoconstrictors. A variety of platelet aggregation inhibitors antagonize platelet responses to wound-generated signals, including ADP, thrombin, and collagen. Anticoagulants disrupt elements of both the intrinsic and extrinsic pathways. Molecular approaches (termed 'sialomics') to characterize the full inventory of mRNAs transcribed in salivary glands have revealed a surprising level of complexity within a single species. Multiple ...
A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.
The penetrance of Lebers hereditary optic neuropathy (LHON) in families with primary mitochondrial DNA (mtDNA) mutations is very complex. Matrilineal and nuclear genetic background, as well as environmental factors, have been reported to be involved in different affected pedigrees. Here we describe two large Chinese families that show a striking difference in the penetrance of LHON, in which 53.3% and 15.0% of members were affected (Pin vivo mitochondrial oxidative metabolism as described in a previous study. Evolutionary analysis failed to indicate any putatively pathogenic mutation that cosegregated with G11778A in these two pedigrees. Our results suggest that the variable penetrance of LHON in the two Chinese families is independent of both their mtDNA haplotype background and a seconda...
Indium sulfide thin films consisting of porous network of nanoplatelets, have been deposited using chemical bath deposition (CBD) method onto the tin-doped indium oxide (ITO) coated glass substrate. Aqueous solutions of indium sulfate and thioacetamide have been used as indium and sulfur precursors. As a complexing agent, acetic acid was used. The chemically deposited indium sulfide thin films were examined for their structural, surface morphological and optical characterizations. The X-ray diffraction analysis revealed the formation of the cubic b-In2S3 onto the substrate. From scanning electron micrograph, it is observed that the surface of substrate is covered by nanoporous platelets type morphology. The optical studies showed a direct band gap of 2.84eV for indium sulfide platelets. Ph...
A protective film has been developed on the surface of carbon steel in low chloride aqueous environment using a synergistic mixture of an environmentally friendly phosphonic acid, N,N-bis(phosphonomethyl) glycine (BPMG), and zinc ions. Impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the chosen environment. Potentiodynamic polarization studies showed that the inhibitor is a mixed inhibitor. X-ray photoelectron spectroscopic analysis (XPS) of the film showed the presence of the elements iron, phosphorus, nitrogen, oxygen, carbon, and zinc. Deconvolution spectra of these elements in the surface film showed the presence of oxides/hydroxides of iron(III), Zn(OH)2, and [Zn(II)-BPMG] complex. This infe...
A complex modulated structure is described for reactive elements that have the capability of considerably more heat than organic explosives while generating a working fluid or gas. The explosive and method of fabricating same involves a plurality of very thin, stacked, multilayer structures, each composed of reactive components, such as aluminum, separated from a less reactive element, such as copper oxide, by a separator material, such as carbon. The separator material not only separates the reactive materials, but it reacts therewith when detonated to generate higher temperatures. The various layers of material, thickness of 10 to 10,000 angstroms, can be deposited by magnetron sputter deposition. The explosive detonates and combusts a high velocity generating a gas, such as CO, and high temperatures. 2 figs.
Proposed features of the competitive electricity market in Ontario were reviewed. The speaker predicted that demand for renewable energy in Ontario`s competitive electricity market will be affected by green power, emissions trading, labelling, and renewables portfolio standard. Under current regulations retailers can charge customers a premium for purchasing electricity generated by `green` sources. The existing limits on emissions of sulphur dioxide, nitrogen oxides and carbon dioxides will remain in place, but an emissions cap and trading program for all Ontario-based generation is an option to consider. Ontario`s Market Design Committee (MDC) has recommended the implementation of emissions trading for electricity-related air pollutants for all generators located in Ontario. The complex mechanics of emission trading are explained. The MDC recommendation of the use of standard labels to disclose the mix of energy sources used by sellers of ...
The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates ...
Ionic conductive materials are of much interest as an electrolyte for solid-state lithium batteries. Poly(alkylene oxide) and lithium salt complex exhibits high ionic conductivity in terms of its high solubility for lithium salts. However, the temperature dependency of its ionic conductivity is quite large and non-linear, the ionic conductivity drops down at low temperature, especially below glass transition temperature of the polymer. Because its ionic conductive mechanism is derived from its segmental motion of polymer main chain. A novel ionic conductive material, poly[2,6-dimethoxy-N-(4-vinylphenyl)benzamide] is synthesized and confirm ionic conductivity even below glass transition temperature. Ionic conductivity of the polymer with lithium ditrifluoromethylsulfonate imide complex shows 10{sup -5}Scm{sup -1} from 0 to 60{sup o}C. Its temperature dependency is linear, namely Arrehnius type dependency. Evaluating from ...
A hydrous oxide film for the application as dielectric film is synthesized by immersion of pure aluminum in hot water. From a Rutherford backscattering analysis, the ratio of aluminum to oxygen atoms was found to be 3:2 in the anodized aluminum oxide film, and 2:1 in the hydrous oxide layer. Anodization of the hydrous oxide layer was more effective for the transition of amorphous anodic oxides to the crystalline aluminum oxides.
The formation of astatide-mercury complexes was investigated in aqueous solutions.The obtained complexes were examined by paper electrophoresis. It was found that Hg(OH)At and Hg(OH)I complexes were formed in neutral solution. The stability constants of the obtained complexes were determined by ion-exchange. The preliminary results indicate that the complex of mercury with astatide is much more stable than similar complexes with iodide. (author)
We consider the problem of minimal (multiplicative) complexity of polynomial multiplication and multiplication in finite extensions of fields. For infinite fields minimal complexities are known [Winograd,...Full Text Available
The oxidative stress theory of aging predicts that manipulations that alter oxidative stress/damage will alter aging. The gold standard for determining whether aging is altered is lifespan,...Full Text Available
Bi-U mixed oxides were synthesized by two methods and characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The samples were tested for the catalytic oxidation of carbon monoxide by oxygen. A stepwise redox mechanism consistent with the kinetic results is proposed. (orig.).
Chemical phase identifications of complex, multilayered corrosion products formed on Fe-Ni-Cr alloys immersed in molten NaNO/sub 3/-KNO/sub 3/ and LiNO/sub 3/-NaNO/sub 3/-KNO/sub 3/ were obtained by X-ray diffraction analysis. Diffraction analyses performed after successive material removal steps provided depth profiles of corrosion products and identified the dominant phases as NaFeO/sub 2/, Fe/sub 3/O/sub 4/, and Cr/sub 2/O/sub 3/ for Alloy 800 and 316SS after immersion in NaNO/sub 3/-KNO/sub 3/. In LiNO/sub 3/-NaNO/sub 3/-KNO/sub 3/, the major corrosion products identified on Alloy 800 were LiFeO/sub 2/, Fe/sub 3/O/sub 4/, and Cr/sub 2/O/sub 3/. X-ray diffraction results were supplemented by electron microprobe analyses that revealed the solid solution nature of several of the oxide phases.
Spent fuel management has always been one of the most important stages in the nuclear fuel cycle and it is still one of the most vital problems common to all countries with nuclear reactors. It begins with the discharge of spent fuel from a power or a research reactor and ends with its ultimate disposition, either by direct disposal or by reprocessing of the spent fuel. Two options exist at present - an open, once-through cycle with direct disposal of the spent fuel and a closed cycle with reprocessing of the spent fuel and recycling of plutonium and uranium in new mixed oxide fuels. The selection of a spent fuel strategy is a complex procedure in which many factors have to be weighed, including political, economic and safeguards issues as well as protection of the environment. Continuous attention is being given by the IAEA to the collection, analysis and exchange of information on spent fuel management. Its role in this area is to provide a ...
Removal of sulfonamide (SAs) and tetracycline (TAs) classes of antibiotic compound from deionized water and DOC water by powdered activated carbon (PAC) adsorption was evaluated in this study. According to the study results, TAs were more easily adsorbed than SAs although TAs were more hydrophilic than SAs. The phenolic compounds in TAs might be responsible for their high adsorption. Complex formation of TAs with metal and metal oxide on the surface of activated carbon might also contribute to higher adsorption. The hydrophobic effect was important for removal of SAs. More hydrophobic SAs were removed more easily. The carbon type was not important for adsorption of SAs and TAs. Coal based carbon and coconut based carbon showed similar removal efficiencies for these antibiotics. Dissolved organic materials interfered with adsorption of SAs and TAs. Organic interference was more significant for the antibiotic compound, which was more subject to ...
Hard surface finishing represents the final manufacturing step for functional areas of machine elements in state-of-the-art production. Raceways of rolling bearing rings are ground and honed to the required low roughness. Plastic deformation is restricted to a narrow edge zone of the hardened steel. Reheating of the machined components below the martensite tempering or bainite transformation temperature results in a marked decrease of the XRD line width on the surface. The investigated samples are made of through-hardened standard bearing steel 100Cr6 (international denotation: SAE 52100). On the basis of a material model that explains the effect as a complex diffusion process of dislocational carbon segregation, i.e. static strain aging, the measured kinetics of the XRD line width reduction is simulated by an Arrhenius-type equation, which describes the rate-controlling reaction step of temper carbide dissolution. The formation of a small white-etching surface ...
This is the final report of a two-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project has examined the fundamental chemistry of plutonium that affects the integration of hydrothermal technology into nuclear materials processing operations. Chemical reactions in high temperature water allow new avenues for waste treatment and radionuclide separation.Successful implementation of hydrothermal technology offers the potential to effective treat many types of radioactive waste, reduce the storage hazards and disposal costs, and minimize the generation of secondary waste streams. The focus has been on the chemistry of plutonium(VI) in solution with carbonate since these are expected to be important species in the effluent from hydrothermal oxidation of Pu-containing organic wastes. The authors investigated the structure, solubility, and stability of the key plutonium complexes. ...
For high-efficiency coal gasification, investigations were given on effect of coal chars with different conversion rates on coal gasification reactivity. In coal gasification, reactivity of char after pyrolysis governs the efficiency. The reference char conversion in CO2 gasification of coal (weight loss) changes linearly in the initial stage of the reaction, but the reactivity declines as the end point is approached. Char surface area is as large as 400 m{sup 2}/g in the initial stage with the conversion at 20%, but it decreases in the final stage. This phenomenon relates closely with changes in pore size and crystalline structure. Change in the Raman value R which shows incompleteness of char graphite structure and amorphous carbon ratio suggests that an active portion with high reactivity is oxidized preferentially, and a portion with low reactivity remains finally. Minerals in coal are known to accelerate the gasification. However, their catalytic effect is ...
This work has been undertaken with a view to study the effect of lanthanum content on properties of PLZT ceramics. The polycrystalline complex compounds of PLZT with Pb{sub 1-x}La{sub x}(Zr{sub 0.40}Ti{sub 0.60}){sub 1-x/4}O{sub 3}, +10% PbO formula were prepared from the nano-size individual oxides powders by hot-pressed process. Transparent PLZT (x/40/60) bulk ceramics with pure tetragonal phase was obtained. The studies of the microstructures, dielectric and ferroelectric properties of the ceramics were carried out. The experiment results showed that when La content increased from 7 to 13 mol.%, the grain size increased from 2 to 7 {mu}m. La content also effects the dielectric property obviously, the dielectric constant increased with La content increasing. Moreover, the ferroelectric properties are sensitive to the variation of La content.
This work has been undertaken with a view to study the effect of lanthanum content on properties of PLZT ceramics. The polycrystalline complex compounds of PLZT with Pb_1_-_xLa_x(Zr_0_._4_0Ti_0_._6_0)_1_-_x_/_4O_3, +10% PbO formula were prepared from the nano-size individual oxides powders by hot-pressed process. Transparent PLZT (x/40/60) bulk ceramics with pure tetragonal phase was obtained. The studies of the microstructures, dielectric and ferroelectric properties of the ceramics were carried out. The experiment results showed that when La content increased from 7 to 13 mol.%, the grain size increased from 2 to 7 #mu#m. La content also effects the dielectric property obviously, the dielectric constant increased with La content increasing. Moreover, the ferroelectric properties are sensitive to the variation of La content.
We study the emission zone in a single-layer polymer light-emitting diode. The emission zone is found by studying the angular distribution of the electroluminescence. The emission is modeled by accounting for optical interference. We account for birefringence of the anode layer in our model. The active polymer was, however, found to be isotropic. The anode consists of a single-layer of the conducting polymer complex poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonate) (PEDOT-PSS), with enhanced conductivity. As a cathode we use plain aluminum. By using only PEDOT-PSS we avoid having a thin metal layer or indium-tin-oxide as the anode in the path of the escaping light. The active material is a substituted polythiophene with excellent film forming properties. A comparison between the experimental and calculated angular distribution of light emission from a single-layered polymer light-emitting diode was shown to be in good agreement for ...
For a better understanding of sulphidation mechanisms, some alloys (alloy 600, alloy 800, Uranus S, iron-chromium-aluminium-alloy) and metals (iron, chromium, nickel, molybdenum, titanium) were tested at 773, 873, 1 073 K in gaseous sulphur dioxide. Total pressure was 760 torrs. Sulphur dioxide pressure was 760, 100 and 10 torrs. Argon, oxygen, water vapor were used, successively, as pressure complement. Oxygen supply, generally speaking cause decay of corrosion resistance in SO/sub 2/ atmospheres especially at 1 073 K with low ratio p/sub O2//P/sub SO/sub 2//. Water vapor supply act similarly. Temperature laws and pressure laws do not give monotonous rise of corrosion values. There are maximas suggesting corrosion products undertaking a volatilization process. According to test conditions, Uranus S, chromium, alloy 800 (and titanium at some extent) showed good corrosion resistance. That results are supporting those obtained by JRC Ispra team, working with sulphuric acid ...
The complex formation of zirconium with biphenyl mono- and biscatecholyazo derivatives has been studied spectrophotometrically. The composition of the complexes, form and charge of complex-forming zirconium ions have been established. A procedure is suggested for calculation of molar absorptivities and stability constants for each of the complexes formed simultaneously in the system. Possible complex formation schemes have been studied. The data obtained were used to develop a spectrophotometric method of determining zirconium in the presence of large amounts of copper.
The effect of hydrogen sulfide (H2S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxidesssuch as iron oxide, nickel oxide, manganese oxide, and copper oxideswas investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H2S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H2S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence ...
Full text of publication follows: Slightly over-stoichiometric lithium orthosilicate pebbles have been selected as one optional breeder material for the European Helium Cooled Pebble Bed (HCPB) blanket. This material has been developed in collaboration of Research Center Karlsruhe and the Schott Glass, Mainz. The lithium orthosilicate pebbles are fabricated from lithium hydroxide and silica by a melting and spraying method in a semi-industrial scale facility. Lithium hydroxide was selected as the precursor since enriched lithium hydroxide is commercially available. The lithium orthosilicate pebbles produced by the process contains oxide phases besides orthosilicate, but it was also found that the oxide phases can be decomposed by annealing at high temperatures. The lithium orthosilicate pebbles produced in this way possesses satisfactory pebble characteristics. Therefore, the authors performed out-of-pile annealing tests using the lithium ...
The valence and spin-state distributions of Co ions and the complex structure of antiferromagnetic Ba_2Co_9O_1_4 have led to the suggestion that doped Ba_2Co_9O_1_4 compounds may be good thermoelectric materials. We have checked this suggestion by measuring the magnetic properties as well as the transport properties of nominal Ba_1_._9A_0_._1Co_9O_1_4 (A=La or Na). We show that although all compounds are indicated to be single phase by powder X-ray diffraction analysis, they are all p-type polaronic conductors with low mobile-hole concentrations. Magnetic-susceptibility data of the parent and La-doped compounds give evidence of a second magnetic phase with ferromagnetic order setting in below 215 K; but this second phase is not seen in the Na-doped sample. We conclude that the structure is stabilized by oxidation and that cation exolution from the Ba_2Co_9O_1_4 structure creates cation vacancies that oxidize the high-spin ...
The hypothesis that intracellular Ca/sup 2 +/ is an essential component of the intracellular mechanism of insulin action in the adipocyte was evaluated. Cells were loaded with the Ca/sup 2 +/ chelator quin-2, by preincubating them with quin-2 AM, the tetrakis(acetoxymethyl) ester of quin-2. Quin-2 loading inhibited insulin-stimulated glucose transport without affecting basal activity. The ability of insulin to stimulate glucose uptake in quin-2-loaded cells could be partially restored by preincubating cells with buffer supplemented with 1.2 mM CaCl/sub 2/ and the Ca/sup 2 +/ ionophore A23187. These conditions had no effect on basal activity and omission of CaCl/sub 2/ from the buffer prevented the restoration of insulin-stimulated glucose uptake by A23187. Quin-2 loading also inhibited insulin-stimulated glucose oxidation and the ability of insulin to inhibit cAMP-stimulated lipolysis without affecting their basal activities. Incubation of cells with 100 ..mu..M ...
The hypothesis that intracellular Ca"2"+ is an essential component of the intracellular mechanism of insulin action in the adipocyte was evaluated. Cells were loaded with the Ca"2"+ chelator quin-2, by preincubating them with quin-2 AM, the tetrakis(acetoxymethyl) ester of quin-2. Quin-2 loading inhibited insulin-stimulated glucose transport without affecting basal activity. The ability of insulin to stimulate glucose uptake in quin-2-loaded cells could be partially restored by preincubating cells with buffer supplemented with 1.2 mM CaCl_2 and the Ca"2"+ ionophore A23187. These conditions had no effect on basal activity and omission of CaCl_2 from the buffer prevented the restoration of insulin-stimulated glucose uptake by A23187. Quin-2 loading also inhibited insulin-stimulated glucose oxidation and the ability of insulin to inhibit cAMP-stimulated lipolysis without affecting their basal activities. Incubation of cells with 100 #mu#M quin-2 or quin-2 AM had no ...
A critical review of the literature revealed no experiments on uranyl ion transfer from an aqueous to a tributyl phosphate phase which positively measured the kinetics of the chemical reaction at the interphase. Drawing isorhythmic lines on a three component diagram gives a complex correlation for the compaction of three sizes of glass beads. Neither the use of thoria sols nor high feed solution concentrations of thorium nitrate gave any significant increase in mean particle diameters over those obtained from nitrate solutions of lower concentrations in flame denitration. A hydraulic film resistance has been detected in the anion exchange of uranyl sulfate into Dowex 2lK, and chloride elution was found to give a higher apparent uranium diffusion coefficient than nitrate elution. The rate of dissolution of mixed thorium-uranium oxides was determined as a function of the per cent of mixed oxides ...
Neurodegeneration observed in Alzheimer disease (AD) is believed to be related to the toxicity from reactive oxygen species (ROS) produced in the brain by the amyloid-{beta} (A{beta}) protein bound primarily to copper ions. The evidence for an oxidative stress role of A{beta}-Cu redox chemistry is still incomplete. Details of the copper binding site in A{beta} may be critical to the etiology of AD. Here we present the structure determined by combining x-ray absorption spectroscopy (XAS) and density functional theory analysis of A{beta} peptides complexed with Cu{sup 2+} in solution under a range of buffer conditions. Phosphate-buffered saline buffer salt (NaCl) concentration does not affect the high-affinity copper binding mode but alters the second coordination sphere. The XAS spectra for truncated and full-length A{beta}-Cu{sup 2+} peptides are similar. The novel distorted six-coordinated (3N3O) geometry around copper in the A{beta}-Cu{sup ...
We studied the interaction of Pu(VI) with Pseudomonas stutzeri ATCC 17588 and Bacillus sphaericus ATCC 14577, representatives of the main aerobic groups of soil bacteria present in the upper soil layers. The accumulation studies have shown that these soil bacteria accumulate high amounts of Pu(VI). The sorption efficiency toward Pu(VI) decreased with increasing biomass concentration due to increased agglomeration of the bacteria resulting in a decreased total surface area and number of available complexing groups. Spores of Bacillus sphaericus showed a higher biosorption than the vegetative cells at low biomass concentration which decreased significantly with increasing biomass concentration. At higher biomass concentrations (> 0.7 g/L), the vegetative cells of both strains and the spores of B. sphaericus showed comparable sorption efficiencies. Investigations on the pH dependency of the biosorption and extraction studies with 0.01 M EDTA solution have shown ...
The use of global three-dimensional (3-D) models with satellite observations of CO2 in inverse modeling studies is an area of growing importance for understanding Earth s carbon cycle. Here we use the GEOS-Chem model (version 8-02-01) CO2 mode with multiple modifications in order to assess their impact on CO2 forward simulations. Modifications include CO2 surface emissions from shipping (0.19 PgC yr 1), 3-D spatially-distributed emissions from aviation (0.16 PgC yr 1), and 3-D chemical production of CO2 (1.05 PgC yr 1). Although CO2 chemical production from the oxidation of CO, CH4 and other carbon gases is recognized as an important contribution to global CO2, it is typically accounted for by conversion from its precursors at the surface rather than in the free troposphere. We base our model 3-D spatial distribution of CO2 chemical production on monthly-averaged loss rates of CO (a key precursor and intermediate in the oxidation of organic ...
Hydroperoxides are important atmospheric oxidants. They are responsible for most of the oxidation of aqueous-phase SO(sub 2) to sulfate in the northeastern United States, resulting in the formation of acid precipitation and visibility-reducing sulfate aerosol (Penkett et al., 1979; Lind et al., 1987; Madronich and Calvert, 1990; Tanner and Schorran, 1995). Atmospheric hydrogen peroxide (H(sub 2)O(sub 2) or HP) is produced by the self-reaction of hydroperoxyl radicals (HO(sub 2)); higher organic peroxides are produced by reaction of HO(sub 2) with alkylperoxyl radicals (RO(sub 2)). Peroxyl radicals, along with OH, are chain carriers in the complex photochemical process that produces tropospheric ozone. Thus, concentrations of peroxides and their free radical precursors depend on solar intensity and ambient concentrations of water vapor, ozone, NO(sub x) (NO+ NO(sub 2)), and VOCs (volatile organic compounds). Several ...
Cyclotomic fast Fourier transforms (CFFTs) are efficient implementations of discrete Fourier transforms over finite fields, which have widespread applications in cryptography and error control codes. They are of great interest because of their low multiplicative and overall complexities. However, their advantages are shown by inspection in the literature, and there is no asymptotic computational complexity analysis for CFFTs. Their high additive complexity also incurs difficulties in hardware implementations. In this paper, we derive the bounds for the multiplicative and additive complexities of CFFTs, respectively. Our results confirm that CFFTs have the smallest multiplicative complexities among all known algorithms while their additive complexities render them asymptotically suboptimal. However, CFFTs remain valuable as they have the smallest overall ...
A spectrophotometric study has been made of the complex formation of vanadium (3) with arsenazo(1), arsenazo(3) and some monosubstituted derivatives of chromotropic acid and sulphanylamides. In acid medium vanadium (3) reacts with each of these reagents to produce a 1:1 complex. Optimum conditions of the complex formation was found. The effect of H"+ on the complex formation of vanadium (3) with chromotropic acid derivatives was established. It was found by the graphical method that the formation of the complex is accompanied by the elimination of one proton. Patterns were found of the influence of the nature of substituents in the organic compound on the ionization constants of acid groups and stability of complexes. Molar extinction coefficients, equilibrium constants of the formation reactions and instability constants for the complexes ...
Oxidation of propylene with oxygen, air and a mixture of nitrogen?oxygen in a barrier discharge is investigated. The selectivity towards formation of propylene oxide in pure oxygen is shown to be as high as 45 wt% and the propylene conversion ratio is found to be 12.9 wt%. In the oxidation with air, the propylene oxide selectivity is 23 wt%, while the conversion is 7.5 wt%. The values of propylene conversion and selectivity towards formation of propylene oxide in a barrier discharge are consistent with those obtained by the thermocatalytic methods for production of propylene oxide.
An investigation of the mechanism of the oxidation and ammoxidation of propylene was made. The products of the above reactions were acrylonitrile and acrolein for ammoxidation and oxidation, respectively. Also, the ammoxidation and oxidation of allyl alcohol, allyl amine, and their allylic deuterium substituted analogues was studied. It was concluded that oxidation and ammoxidation of propylene have the same rate determining step. Other conclusions about the reaction intermediates were also made.
The electrochemical oxidation as a method to destroy drug residues like Aspirin {sup trademark}, tetracycline or gentamicin in water was investigated with C-Anode (modified by manganese oxides) and Pt Anode. The mechanism of Aspirin {sup trademark} and tetracycline oxidation and the influence of the biocide effect was observed using GC-MS and three different microbiological tests. In general the biological availability increases with progressive oxidation of the antibiotics. (orig.)
Halide complexes of astatine cations At"+ and AtO"+ were prepared and their rate of migration was measured. The complexes are of the type AtX_2"- and AtOX_2"- (X = Cl"-, Br"-, I"-). The bromo complexes, AtBr_2"- and AtOBr_2"-, have a higher stability than the chloro complexes. The hydrolysis in weakly alkaline solution of AtX_2"- resulted At"-, and that of AtOX_2"- AtO_2"-. (author).
The widely accepted oxidative stress theory of aging postulates that aging results from accumulation of oxidative damage. Surprisingly, data from the longest-living rodent known, naked mole-rats [MRs;...Full Text Available
Background. The Free Radical Theory of Aging mechanistically links oxidative stress to aging. Okinawa has among the world's longest-lived populations but oxidative stress in this...Full Text Available
Oxidative stress occurs when the level of prooxidants exceeds the level of antioxidants in cells resulting in oxidation of cellular components and consequent loss of cellular function. Oxidative...Full Text Available
1. Nitric oxide generation is important in the regulation of resistance vessel tone. Until now, however, there has been no evidence of such a role for basal generation of nitric oxide in the skin microcirculation...Full Text Available
The catalytic effects of copper-aluminium-magnesium oxides in the oxidative coupling of phenylethyne is described. The importance of surface properties as a redox site are discussed.
Studies were conducted to quantitate the evolution of nitrogen oxides (NO(x)) from soybean [Glycine max (L.) Merr.] leaves during in vivo nitrate reductase...Full Text Available
Potato tuber mitochondria oxidizing malate respond to NAD+ addition with increased oxidation rates, whereas mung bean hypocotyl mitochondria do not. This is traced to a low endogenous content...Full Text Available
The potential for oxidation of ammonia in anoxic marine sediments exists through anaerobic oxidation by Nitrosomonas-like organisms, utilizing nitrogen dioxide, coupling of nitrification,...Full Text Available
BackgroundHigh complexity is considered a hallmark of living systems. Here we investigate the complexity of temporal gene expression patterns using the concept of Permutation Entropy...Full Text Available
The CCR4-NOT complex is the main enzyme catalyzing the deadenylation of mRNA. We have investigated the composition of this complex in Drosophila melanogaster by immunoprecipitation...Full Text Available
Target of rapamycin (TOR) kinases control cell growth through two functionally distinct multiprotein complexes. TOR complex 1 (TORC1) controls temporal cell growth and is sensitive to rapamycin, whereas...Full Text Available
During the past 3 years, progress was made in elucidating the excited state structures of Pt(diimine)(dithiolate) complexes, while more recent efforts focused on the photochemistry of these complexes and electronic structure of other dithiolate systems. A carbonyl-Ir-maleonitrile dithiolate complex is also studied.
BackgroundIn this study we investigated the predictability of three thermodynamic quantities related to complex formation. As a model system we chose the host-guest complexes of...Full Text Available
Ligand exchange of hydrated metal complexes is common in chemical and biological systems. Using the ultrafast T-jump, we examined this process, specifically the transformation of aqua cobalt (II) complexes...Full Text Available
The Δ- and Λ-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a...Full Text Available
Apparatus and method for selective measurement of tritium oxide in an environment which may include other radioactive components and gamma radiation, the measurement including the selective separation of tritium oxide from a sample gas through a membrane into a counting gas, the generation of electrical pulses individually representative by rise times of tritium oxide and other radioactivity in the counting gas, separation of the pulses by rise times, and counting of those pulses representative of tritium oxide. The invention further includes the separate measurement of any tritium in the sample gas by oxidizing the tritium to tritium oxide and carrying out a second separation and analysis procedure as described above.
The theoretical principles underlying the formation of oxide and, in particular, anodic oxide coatings on metals produced by chemical oxidation, anodizing in solutions, and anodizing in cold plasmas are reviewed. The mechanisms and conditions of anodic oxidation are described, and the structure of anodic oxide coatings on aluminum, magnesium, beryllium, zinc, cadmium, iron, cobalt, nickel, titanium, zirconium, tantalum, and chromium alloys is examined. Attention is also given to various applictins of anodized coatings. 54 references.
The potential use of uranium in the field of catalysis is presented in the first part of this paper. Numerous applications of uranium binary oxides, as well as mixed oxides, are reviewed with a special emphasis on the role of U-Sb-O catalysts in selective oxidation (and ammoxidation) processes. Attempts are made to correlate the electronic structure of uranium, and especially the role that 5f electrons play in bonding, with its promising catalytic properties. In the second part, new data are given for uranium-bismuth mixed oxides in the catalytic oxidation of CO by O_2. Kinetic tests performed in a flow microreactor allow a mechanism to be proposed that involves the direct participation of lattice oxygen of the catalyst in the chemical process (redox mechanism). The high activity can be related to the ability of uranium to change reversibly its oxidation state. ...
The growth of an oxide interfacial layer was recently found to increase the open-circuit voltage (OCV) and efficiency by up to 60 per cent in GaAs metal-semiconductor solar cells. Details of oxidation techniques to provide the necessary oxide thickness and chemical structure and using ozone, water-vapor-saturated oxygen, or oxygen gas discharges are described, as well as apparent crystallographic orientation effects. Preliminary results of the oxide chemistry obtained from X-ray, photoelectron spectroscopy are given. Ratios of arsenic oxide to gallium oxide of unity or less seem to be preferable. Samples with the highest OVC predominantly have As(+3) in the arsenic oxide rather than As(+5). A major difficulty at this time is a reduction in OCV by 100-200 mV when the antireflection coating is vacuum deposited.
The potential use of uranium in the field of catalysis is presented in the first part of this paper. Numerous applications of uranium binary oxides, as well as mixed oxides, are reviewed with a special emphasis on the role of U-Sb-O catalysts in selective oxidation (and ammoxidation) processes. Attempts are made to correlate the electronic structure of uranium, and especially the role that 5f electrons play in bonding, with its promising catalytic properties. In the second part, new data are given for uranium-bismuth mixed oxides in the catalytic oxidation of CO by O/sub 2/. Kinetic tests performed in a flow microreactor allow a mechanism to be proposed that involves the direct participation of lattice oxygen of the catalyst in the chemical process (redox mechanism). The high activity can be related to the ability of uranium to change reversibly its oxidation ...
PurposeCataracts are often considered to be an unavoidable consequence of aging. Oxidative damage is a major cause or consequence of cortical and nuclear cataracts, the most common...Full Text Available
Ethane oxidation was studied in ethane-grown resting cells (mycelia) of an Acremonium sp. and in cell-free preparations of such mycelia. From resting cell experiments evidence was found for a pathway...Full Text Available
Metastable yttrium-oxide films are synthesized using reactive sputter deposition. The yttrium concentration of the as-deposited film is found to vary as a function of the sputter deposition rate. In addition to the synthesis of the cubic equilibrium phase...
Alkali metal doped double perovskites containing manganese and at least one of cobalt, iron and nickel are useful in the oxidative coupling of alkane to higher hydrocarbons.
This patent describes a catalyst composition. It consists of the catalytic oxides of iron, bismuth, molybdenum and magnesium as essential components and optionally the oxides of cobalt, nickel, phosphorus and arsenic.
Background:To determine nutrient requirements by the carbon oxidation techniques, it is necessary to know the fraction of carbon dioxide produced during the oxidative...Full Text Available
May 31, 2011 ... A Theoretical Solid Oxide Fuel Cell Model for System Controls and Stability Design AUTHOR(S): Kopasakis, George; Brinson, Thomas; Credle, ...
In an effort to develop octahedral metal complexes as chemotherapeutic and diagnostic agents targeted to DNA, it is critical to optimize the properties of their cellular uptake. Appending d-octaarginine...Full Text Available
Platinum(II) complexes have been investigated in the hydration of alkynes. These catalysts offer improved regioselectivity over Hg(II) counterparts. 1 fig., 2 tabs.
The synthesis, crystal structure, thermal stability and absorbance spectra of perovskite-type oxynitrides with the general formula SrTi1-xNbx(O,N)3 (x=0.05, 0.10, 0.20, 0.50, 0.80, 0.90, 0.95) have been investigated. Oxide samples were prepared by a polymerized complex synthesis route and post-treated under ammonia at 850 oC for 24 h to substitute nitrogen for oxygen. Synchrotron X-ray powder diffraction (XRD) evidenced that the mixed oxide phases were all transformed into oxynitrides with perovskite-type structure during a thermal ammonolysis. SrTi1-xNbx(O,N)3 with compositions x?0.80 crystallized in a cubic and samples with x?0.90 in a tetragonal structure. The Rietveld refinement indicated a continuous enlargement of the lattice parameters towards higher niobium content of the samples. Thermogravimetric analysis (TGA) and hotgas extraction revealed the dependence of the nitrogen incorporation upon the degree of niobium ...
Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (mu XRF), X-ray absorption spectroscopy (mu EXAFS), and X-ray diffraction (mu XRD) in conjunction with focused ion beam (FIB) sectioning, and highresolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary ...
Red mud is a waste product of the aluminium refining industry. It is composed of aluminium hydroxide and iron oxide. This study examined the feasibility of using red mud as a catalyst to eliminate volatile organic compounds in atmospheric pollutants. Volatile organic compounds can be eliminated by thermal oxidation between 600 and 1100 degrees C. However, the oxidation of volatile organic compounds can also be accomplished at lower temperatures (200 to 450 degrees C) if a catalyst is present. Currently, the low temperature destruction of volatile organic compounds is not widespread because of the difficulty in deactivating the catalyst. In this study, red mud was calcined in air at 500 degrees C. Under such conditions, the red mud converts to aluminium oxide and iron oxide. These 2 oxides are active and are carbon dioxide selective in the ...
The influence of MeV electrons irradiation on the gate oxide layers of hydrogenated polysilicon thin film transistors (TFTs) was investigated by measuring gate leakage currents and threshold voltages. The experimental data revealed a decrease of oxide trap density and increase of positive oxide charge. Improvement in the interface roughness and in the oxide quality near the bottom interface was observed.
The influence of MeV electrons irradiation on the gate oxide layers of hydrogenated polysilicon thin film transistors (TFTs) was investigated by measuring gate leakage currents and threshold voltages. The experimental data revealed a decrease of oxide trap density and increase of positive oxide charge. Improvement in the interface roughness and in the oxide quality near the bottom interface was observed.
We report on the fouling of Focused Ion Beam (FIB)-fabricated silicon oxide nanopores after exposure to tap water for two weeks. Pore clogging was monitored by Scanning Electron Microscopy (SEM) on both bare silicon oxide and chemically functionalized nanopores. While fouling occurred on hydrophilic silicon oxide pore walls, the hydrophobic nature of alkane chains prevented clogging on the chemically functionalized pore walls. These results have implications for nanopore sensing platform design.
By means of ESCA the composition and the thickness of passive films formed on austenitic stainless steels were investigated after the attack of nitric acid at various temperatures and acid concentrations. The outermost layers of the oxide film consist of SiO_2, then a layer rich of Cr-oxid follows, containing also some Mo in the four- and sixvalent state. Ni does not contribute to the oxide film. Cr is also enriched in the metal just below the oxide film. (orig.).
The RKR potential energy curves are constructed for the ground states of diatomic hafnium oxide and thorium oxide. Using Lippincott and Hulburt-Hirschfelder potential function the dissociation energies are estimated by curve fitting method. The H-H potential function was found to give a better fit in both cases. The dissociation energies of hafnium oxide and thorium oxide are estimated as 9.04 #+-# 0.02 eV and 10.34 #+-# 0.01 eV respectively. (author).
Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl chloride was ...
Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl chloride was ...
Basic research of the structure and electronic properties of a-Si:H is reported with particular emphasis on the role of defects. The main findings are as follows: (1) low defect density material can be deposited at a high rate using SiH/sub 4/ diluted in He or Ne. Using Ar or Kr results in a high defect density and columnar material; (2) an electrical bias during deposition modifies the band gap, hydrogen concentration and structure; (3) the clustering of hydrogen in the regions between the columns is confirmed; (4) hydrogen diffusion is observed by NMR; (5) the oxidation of an a-Si:H surface results in approx. 3 x 10/sup 11/ cm/sup -2/ dangling bonds at the interface; (6) auger recombination of photoexcited carriers is a significant non-radiative mechanism at low temperatures; (7) non-radiative recombination by diffusion and capture at dangling bonds is observed at temperatures above 50 to 100/sup 0/K; (8) the defect density in doped and compensated a-Si:H is ...
The penetrance of Leber's hereditary optic neuropathy (LHON) in families with primary mitochondrial DNA (mtDNA) mutations is very complex. Matrilineal and nuclear genetic background, as well as environmental factors, have been reported to be involved in different affected pedigrees. Here we describe two large Chinese families that show a striking difference in the penetrance of LHON, in which 53.3% and 15.0% of members were affected (P < 0.02), respectively. Analysis of the complete mtDNA genome of the two families revealed the presence of the primary mutation G11778A and several other variants suggesting the same haplogroup status G2a. The family with higher penetrance contained a previously described secondary mutation G13708A, which presents a polymorphism in normal Chinese samples and does not affect in vivo mitochondrial oxidative metabolism as described in a previous study. Evolutionary analysis failed to indicate any ...
The penetrance of Leber's hereditary optic neuropathy (LHON) in families with primary mitochondrial DNA (mtDNA) mutations is very complex. Matrilineal and nuclear genetic background, as well as environmental factors, have been reported to be involved in different affected pedigrees. Here we describe two large Chinese families that show a striking difference in the penetrance of LHON, in which 53.3% and 15.0% of members were affected (P < 0.02), respectively. Analysis of the complete mtDNA genome of the two families revealed the presence of the primary mutation G11778A and several other variants suggesting the same haplogroup status G2a. The family with higher penetrance contained a previously described secondary mutation G13708A, which presents a polymorphism in normal Chinese samples and does not affect in vivo mitochondrial oxidative metabolism as described in a previous study. Evolutionary analysis failed to indicate any putatively ...
In this experiments, we established long-termed culture methods of bone marrow stromal cells for proliferation and differentiation of stem cells. And we selected some extracts which support maximal proliferation of stromal cells with this method. We conformed the synergic effects of herval mixture extracts for stromal cell growth. The proliferation of stromal cells was increased rather by the addition of mixture extracts than by addition of single strain extract. In the previous and cooperative experiments, we selected complex extracts which increased the number of nonadherent mononuclear cells. Different cytokine expression patterns were observed stromal cells cultured in the presence or absence of mixture extracts which support differentiation of nonadherent cells. Stimulation of macrophage cell line with herval extracts with the treatments of recombinant interferon-{gamma} resulted in increased nitric oxide synthesis in a dose-dependent ...
The complex phase relationships near the BaO-poor region of the quaternary Ba-Sm-Y-Cu-O oxide system prepared in pure air (pO2=22 kPa, 950 oC) and in 0.1% O2 (pO2=100 Pa, 810 oC) have been determined. This investigation also included the subsolidus compatibilities in ten subsystems (Ba-Sm-Y-O, Ba-Sm-Cu-O, Ba-Y-Cu-O, Sm-Y-Cu-O, Ba-Sm-O, Ba-Y-O, Ba-Cu-O, Sm-Y-O, Sm-Cu-O, and Y-Cu-O), and the homogeneity range of five solid solutions (Ba(SmxY2-x)CuO5, (Sm,Y)2O3, (Sm,Y)2CuO4, (Y,Sm)2Cu2O5, and Ba(Sm,Y)2O4). The single phase range of the superconductor solid solution, (Ba2-xSmx)(Sm1-yYy)Cu3O6+z, and the phase compatibilities in its vicinity, which are particularly important for processing, are described in detail. The phase equilibrium data of the Ba-Sm-Y-Cu-O system will enable the improvement of the intrinsic superconducting properties of second-generation wires, and facilitate the flux-pinning process. -- Graphical Abstract: Phase diagram ...
The modification of polymers by radiation grafting has been utilized for several decades. The penetrability of gamma rays allows to modify the internal surfaces of porous materials retaining its mechanical properties. In recent years applications of these materials to obtain chromatographic supports and biocatalysts have been reported. In this work, we described the grafting of glycidyl methacrylate (GMA) onto a macroporous polysulfone polymer. Reproducible amount of grafting, from 10% to 60% was obtained by choosing favourable monomer concentration and gamma radiation doses from 6 kGy up. Afterwards, iminodiacetic acid (IDA) and amino phenyl arsine oxide (PAO) were covalently attached to the grafted polyGMA, in correspondence with the grafting degree. Later on, a recombinant histidin-patch thioredoxin protein (HP-rTrx) was immobilized onto this surface by two different ways, involving specific protein orientations. The first one involves an IDA-Ni{sup 2+} ...
This paper discusses a new type of supramolecular material tris{5-N-[3-(9H-carbazol-9-yl)propyl]-N-(4-methylphenyl) aminesulfonyl-8-hydroxyquinolato} aluminum(III), Al(SCarq)3, which we synthesized using three 5-N-[3-(9H-carbazol-9-yl)propyl]-N-(4-methylphenyl) aminesulfonyl-8-hydroxyquinoline as bidentate ligands. The peak photoluminescence in the solid phase appears at 488 nm. In cyclic voltammetric measurement, two oxidation peaks, which were obtained at -5.6 and -5.9 eV, correspond to HOMO sites of carbazoyl and aluminum quinolates, respectively. In the investigation of solid morphological thin film, the flat surface was investigated using an atomic force microscope. The root mean square (rms) and mean roughness (Ra) were respectively measured to be 0.427 and 0.343 nm. For the fabrication of organic light-emitting devices (OLEDs) using spin-coating techniques, the turn-on voltage and maximum luminescence of the optimized electroluminescence device, glass/ITO ...
The study of tropospheric kinetics underlies global change because key greenhouse gases are photochemically active. Modeling of tropospheric chemistry on a global scale is essential because some indirect greenhouse gases are short-lived and interact in a non-linear fashion. It is also extremely challenging, however; the global change grid is extensive in both the physical and temporal domains, and critical lower atmospheric species include the organics and their oxidized derivatives, which are numerous. Several types of optimization may be incorporated into kinetics modules to enhance their ability to simulate the complete lower atmospheric gas phase chemical system. (1) The photochemical integrator can be accelerated by avoiding matrix and iterative solutions and by establishing families. Accuracy and mass conservation are sacrificed in the absence of iteration, but atom balancing is restorable post hoc. (2) Chemistry can be arranged upon the massive grid to ...
Irradiation is efficient at extinction fungi contamination in peanuts. Peanuts have high biologic value protein, minerals, vitamin E, complex B, and high concentration of lipids. The objective of this research is to evaluate the gamma irradiation effect on color, total phenolic, antioxidant activity, and fatty acid profile in peanuts (Arachis hypogaea L.). Cultivars IAC-Tatu ST and IAC-Runner 886 were submitted to gamma radiation with doses of 5.0; 7.5; 10.0, and 15.0 kGy and storage at room temperature. There was no significant difference in the color of IAC-Tatu ST. However, significant difference was found in the luminosity and Chroma in IAC-Runner 886. Total fenolics differed from the control with 33.27 mg.g-1 and treatment dose of 10.0 kGy with 58.60 mg.g-1 in IAC-Tatu ST. This parameter not had significant difference in IAC-Runner 886 and the control with 51.59 mg.g-1. The antioxidant activity did not present significant difference with a dose of 10.0 kGy, ...
Radiation sterilization has several merits that it is a positively effective sterilization method, it can be used to sterilize low heat-resistant containers and high gas barrier films, and there is no possibility of residual chemicals being left in the packages. It has been commercially used in 'Bag in a Box' and some food containers. The #gamma# ray and an electron beam are commonly used in radiation sterilization. The #gamma# ray can sterilize large size containers and containers with complex shapes or sealed containers due to its strong transmission capability. However, since the equipment tends to be large and expensive, it is generally used in off production lines. On the other hand, it is possible to install and electron beam system on food production lines since the food can be processed in a short time due to its high beam coefficient and its ease of maintenance, even though an electron beam has limited usage such as sterilizing relatively thin materials ...
The physicochemical forms and partitioning of corrosion products released from stainless steel upon exposure to selected environmental conditions is the subject of this investigation. This report describes the influence of calcareous sediment on the rate of release and fate of corrosion products produced when neutron-activated stainless steel specimens were exposed to a Globigerina ooze taken from the Northeast Pacific Ocean. The calcareous ooze used in this study consists largely of planktonic formanifera tests and was found to be about 90% CaCO_3. The trace metal content of this sediment was typical of average deep-sea carbonate sediments, and the ratios of trace elements to Ti were not remarkably different from a coastal clayey silt or a Northeast Pacific pelagic red clay. Most (>80%) of the trace metals extracted by sequential chemical treatment were associated with reductant-soluble materials, i.e., amorphous Mn and Fe oxides, or were incorporated in the ...
In this experiments, we established long-termed culture methods of bone marrow stromal cells for proliferation and differentiation of stem cells. And we selected some extracts which support maximal proliferation of stromal cells with this method. We conformed the synergic effects of herbal mixture extracts for stromal cell growth. The proliferation of stromal cells was increased rather by the addition of mixture extracts than by addition of single strain extract. In the previous and cooperative experiments, we selected complex extracts (Him-I, Him-II) which increased the number of nonadherent mononuclear cells. Different cytokine expression patterns were observed stromal cells cultured in the presence or absence of mixture extracts which support differentiation of nonadherent cells. Some fractions of Him-I and Him-II increased the proliferation of bone marrow cells irradiated {gamma}-ray(4Gray). Stimulation of macrophage cell line with herval extracts with the ...
The reverse micelle catalyst preparation method has been used to prepare catalysts on four supports: magnesium oxide, carbon, alumina- titania and steamed Y zeolite. These catalysts were not as active as a reference catalyst prepared during previous contracts to Union Carbide Corp. This catalyst was supported on steamed Y zerolite support and was impregnated by a pore-filling method using a nonaqueous solvent. Additional catalysts were prepared via pore- filling impregnation of steamed Y zeolites. These catalysts had levels of cobalt two to three and a half times as high as the original Union Carbide catalyst. On a catalyst volume basis they were much more active than the previous catalyst; on an atom by atom basis the cobalt was about of the same activity, i.e., the high cobalt catalysts` cobalt atoms were not extensively covered over and deactivated by other cobalt atoms. The new, high activity, Y zerolite catalysts were not as stable as the earlier Union Carbide ...
Over one-third of Canada's coal resources occurs in the southern Canadian Rocky Mountains, with major deposits in the Front Ranges, Inner Foothills and Outer Foothills. In the Front Ranges, deposits of metallurgical and thermal, high-volatile bituminous to semi-anthracite coal occur in the Late Jurassic-Early Cretaceous Mist Mountain Formation. In the Inner Foothills of northeastern British Columbia and west-central Alberta, resources of metallurgical and thermal medium- and low-volatile bituminous coal occur in Early Cretaceous strata of the Gething and Gates Formations. In the Outer Foothills resources of thermal, high-volatile bituminous coal occur in Late Cretaceous and Paleocene strata of the Belly River Coalspur and Paskapoo Formations. The major deposits of the Front Ranges and Inner Foothills accumulated within the coastal plains of the Fernie and Moosebar-Clearwater seas. Shorelines prograded to the north and northeast into a foreland basin that evolved in advance of ...
The use of Chelex resin for the synthesis of radioactive lead complexes has been explored. The process involved immobilization of {sup 203}Pb on the resin and subsequent elution of complexed lead by chelating agents. {sup 203}Pb complexes derived from meso- and racemic dimercaptosuccinic acid (meso-DMSA, rac-DMSA) were prepared and assessed for stability in vitro.
The use of Chelex resin for the synthesis of radioactive lead complexes has been explored. The process involved immobilization of "2"0"3Pb on the resin and subsequent elution of complexed lead by chelating agents. "2"0"3Pb complexes derived from meso- and racemic dimercaptosuccinic acid (meso-DMSA, rac-DMSA) were prepared and assessed for stability in vitro.
Given a countable set X (usually taken to be the natural numbers or integers), an infinite permutation, \\pi, of X is a linear ordering of X. This paper investigates the combinatorial complexity of infinite permutations on the natural numbers associated with the image of uniformly recurrent aperiodic binary words under the letter doubling map. An upper bound for the complexity is found for general words, and a formula for the complexity is established for the Sturmian words and the Thue-Morse word.
Dithiolato-nickel complexes with multisulfur ligands derived from benzenehexathiolate have been synthesized. The properties of the monomeric and polymeric complexes have been characterized by ESR spectroscopic and magnetochemical data and by electrical conductivity measurements. The prepared complexes are paramagnetic and have characteristic absorptions between 800 and 1000 nm. (orig.).
The complexing of paramagnetic salts of molybdenum and tungsten with tri-tert-butylphenyl ester of 1,2-naphthoquinone-diazide-(2)-5-sulfochloride is studied by PMR and EPR methods. From the changes of half-widths of lines in PMR spectra and analysis of g-factor in EPR spectra, the kinetic and thermodynamic parameters of the complexing are determined, and the composition of the complexes formed is established, and the schemes of their formation are suggested.
The effect of sodium on the partial oxidation of methane over MoO{sub 3}-SiO{sub 2} in the presence of molecular oxygen has been investigated. As in the sodium-free case, the major products are formaldehyde, carbon monoxide, carbon dioxide, and water. Kinetic analysis indicates that methane is directly oxidized to formaldehyde and carbon dioxide. Formaldehyde is oxidized to carbon monoxide, which is itself further oxidized, providing an alternative route to carbon dioxide. The kinetic model shows that sodium poisons the direct oxidation of methane to formaldehyde and carbon dioxide, but promotes the oxidation of formaldehyde and carbon monoxide. Model predictions of rates and selectivities are in good agreement with the experimental data. A mechanism that explains both the poisoning and promotion effects of sodium on MoO{sub 3}-SiO{sub 2} is proposed.
Targets for heterogeneous transmutation of americium are composed of a support material, the inert matrix and of an americium oxide compound: AmO{sub 2-x} or Am{sub 2}O{sub 3}. In parallel to the studies using americium, simulated compounds of americium oxide, chosen amongst lanthanide oxides, are used. The selection of these compounds is based on theoretical, physical and crystallochemical considerations. In order to assess the influence of impurities composed of lanthanide oxides, resulting from the separation process, on the physical and chemical properties of such a target, synthesis of oxide powders containing impurities associated with the simulated americium oxide, characterizations, crystallographic studies and sodium compatibility tests have been performed. (author)
Titanium oxides were grown anodically to selected final potentials on grade II polycrystalline titanium under different anodization rates. XPS and RBS results show that the oxide consists of primarily TiO2 with a non-stoichiometric oxide/metal interface, with the slower growth rate associated with a thicker layer at the interface. Characterization using TEM reveals that the structure of the oxide evolves from a primarily amorphous phase to islands of crystallites in an amorphous matrix, to an entirely crystalline phase by increasing the polarization potential. Slower growth rates tend to remain crystalline at higher potentials. The mechanical strength of oxide films extracted from load-depth data by nanoindentation varies dramatically for oxide films grown by different rates at 9.4 V, and to a lesser extent at lower potentials. The variation of film strength is ...
Desulphurization of gasoline and kerosene was carried out using organic and inorganic oxidants. Among the organic oxidants used were hydrogen peroxide in combination with acetic acid, formic acid, benzoic acid and butyric acid, while inorganic oxidants used included potassium permanganate and sodium perchlorate. The oxidation of each petroleum oil was carried out in two steps; the first step consisted of oxidation of the feed at moderate temperature and atmospheric pressure while in the second step, the oxidized mixture was extracted with azeotropic mixture of acetonitrile-water. A maximum desulphurization has occurred with NaClO4 and hydrogen peroxide and acetic acid, which are 68% and 61%, respectively in case of gasoline and 66% and 63%, respectively in case of kerosene oil. The FTIR st...
A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)
This paper describes the search for new potential chemotherapeutic agents based on transition metal complexes with planar ligands. In this study, palladium polypyridyl complexes were synthesized and characterized by elemental analysis, NMR, UV-VIS and IR spectroscopies. The interaction of the complexes with DNA was also investigated by spectroscopic methods. All metal-to-ligand charge transfer (MLCT) bands of the palladium polypyridyl complexes exhibited hypochromism and red shift in the presence of DNA. The binding constant and viscosity data suggested that the complexes [PdCl{sub 2}(phen)] and [PdCl{sub 2}(phendiamine)] interact with DNA by electrostatic forces. Additionally, these complexes induced an important leishmanistatic effect on L. (L.) mexicana promastigotes at the final concentration of 10 {mu}mol L{sup -1} in 48 h. (author)
Spectrophotometric methods were used to investigate the properties of neptunium(VII), (VI), and (V) in silicate solution. The transition of cationic neptunium(VII) to anionic species in non-complexing environments proceeds in the range of ?? 5.5 to 7.5. In the presence of carbonate, this transition occurs at ?? 10.0 to 11.5 and in silicate solutions at ?? 10.5-12.0. These findings show that cationic neptunium(VII) forms complexes with both carbonate and silicate and that the silicate complex is stronger than that of the carbonate. The competition of complex formation reactions for neptunium(VI) with carbonate and silicate and on the known complex stability constant of NpO2(CO3)34- allowed the NpO2SiO3 complex stability constant, log ? = 16.5, to be estimated. Determination of the formation constant of Np(V) complexes with SiO32- was not ...
The work identifies the first lattice decoding solution that achieves, in the general outage-limited MIMO setting and in the high-rate and high-SNR limit, both a vanishing gap to the error-performance of the (DMT optimal) exact solution of preprocessed lattice decoding, as well as a computational complexity that is subexponential in the number of codeword bits. The proposed solution employs lattice reduction (LR)-aided regularized (lattice) sphere decoding and proper timeout policies. These performance and complexity guarantees hold for most MIMO scenarios, all reasonable fading statistics, all channel dimensions and all full-rate lattice codes. In sharp contrast to the above manageable complexity, the complexity of other standard preprocessed lattice decoding solutions is shown here to be extremely high. Specifically the work is first to quantify the complexity of these lattice ...
Our goal was a process to convert methane to higher hydrocarbons oxidatively, since this circumvents thermodynamic yield limits of a strictly degydrogenative process. Keller and Bhasin converted thermodynamic yield limits of a strictly dehydrogenative process. Keller and Bhasin converted methane to higher hydrocarbons by using metal oxides as oxidants, without co-fed oxygen. They stated that selectivity is necessarily poor if gaseous oxygen is present. Jones and Sofranko have also used reducible metal oxides as oxidants in a group of their parents, but later used some of those materials with continuous O{sub 2} feed without much loss of selectivity. Baerns, Lunsford and Otsuka have shown that high selectivity could be possible with co-fed O{sub 2} at least for low O{sub 2} partial pressures, over PbO-A1{sub 2}O{sub 3}, Li-MgO and rare earths. The performance of a group of ...
The oxidative dehydrodimerization of propylene to C/sub 3/-dimers (1,5-hexadiene and benzene) has been examined at 600/sup 0/C and atmospheric pressure using a (Bi/sub 2/O/sub 3/)/sub 0.85/(La/sub 2/O/sub 3/)/sub 0.15/ oxide ion-conducting catalyst in a reactor where a catalyst disk separates a feed of propylene in helium from air. The surface of the disk exposed to propylene was reoxidized not by gaseous O/sub 2/, but by the dissociative adsorption and reduction of dioxygen at the oxidant side of the disk, followed by oxide ion conduction to replace spent lattice oxygen. Selectivity to C/sub 3/-dimers when using lattice oxide migration to reoxidize the catalyst was considerably greater than when O/sub 2/ was added to the propylene feed under the same reaction conditions. This result supports the proposal that lattice oxygen is predominantly involved in the selective ...
Data are presented on the insulating properties and capacitance-voltage (CV) characteristics of metal-oxide-semiconductor (MOS) device-thickness (below approx. 100 nm) native oxides formed by wet thermal oxidation of thin InAlP epilayers lattice matched to GaAs. Low leakage current densities of J=1.4 x 10-9 A/cm2 and J=8.7 x 10-11 A/cm2 are observed at an applied field of 1 MV/cm for MOS capacitors fabricated with 17 nm and 48 nm oxides, respectively. TEM images show that the In-rich interfacial particles which exist in 110 nm oxides are absent in 17 nm oxide films. Quasi-static capacitance-voltage measurements of MOS capacitors fabricated on both n-type and p-type GaAs show that the InAlP oxide-GaAs interface is sufficiently free of traps to support inversion, indicating an unpinned Fermi level. These data suggest that InAlP native ...
This work reports studies of ethanol oxidation on Pt-Sn/C catalysts with nearly the same particle size and identical overall composition having different amounts of oxide and alloyed phases. Results of characterization of physical properties by transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), and in situ dispersive X-ray absorption spectroscopy (DXAS) are presented. The variation in the amount of oxide and alloyed phases, promoted by heat treatments in mild temperature conditions, does not produce any significant particle growth. Cyclic voltammetry and oxidation of adsorbed CO in acid medium are used to probe the surface conditions. Data on the electrocatalytic activity towards ethanol oxidation, obtained by potential sweeps and chronoamperometry, are discussed and correlate well with ...
Modification of DNA and double-stranded deoxyoligonucleotides with antitumor 1,2-diamino-cyclohexanedinitroplatinum(II) (Pt-dach) complexes was investigated with the aid of physico-chemical methods and chemical probes of nucleic acid conformation. The three Pt-dach complexes were used which differed in isomeric forms of the dach non-leaving ligand-Pt(1R,2R-dach), Pt(1S,2S-dach) and Pt(1R,2S-dach) complexes. The latter complex has lower antitumor activity than the other two Pt-dach complexes. Pt(1R,2S-dach) complex exhibits the slowest kinetics of its binding to DNA and of the conversion of monofunctional binding to bifunctional lesions. The anomalously slow electrophoretic mobility of multimers of the platinated and ligated oligomers suggests that bifunctional binding of Pt-dach complexes to a d(GG) site within double-stranded ...
The aim of this paper is to investigate the total ionizing dose (TID) radiation effects on MOS capacitor with nitride/oxide stack gate. The stack gate MOS capacitors are fabricated with 20 nm oxide, 40 nm nitride or 110 nm nitride respectively. Through the analysis of CV curve of the irradiation capacitors, it is found that the degradation of the CV curve is due to a significant increase of interface traps and somewhat smaller oxide charge. It is also shown that the thicker of the nitride, more interface traps and oxide charge will be occurred. (authors)
The procedure of charge-coupled devices (CCD) are investigated by using MOS capacitors for enhancing their ionizing radiation tolerance. Authors have found that the gate oxidation temperature, thickness of SiO_2 gate insulator and high temperature processes after gate oxidation are crucial for determining the radiation tolerance of the devices, and proposed to decrease the thickness of gate insulator, perform gate oxidation at 1000 deg C by means of dry oxidation and minimize the number of high temperature procedure steps after gate oxidation. All stated above is a necessary preparation for priducing radiation hardened charge-coupled devices.
SiSiC is one of selected materials for the thermal chemical hydrogen production IS (Iodine-Sulfur) process at JAERI. SiSiC was tested in boiling sulfuric acid for 1000 hours. The obtained results showed the following facts. The transverse strength was not changed by sulfuric corrosion, high temperature oxidation and oxidation. Silica scale formed on SiSiC by sulfate corrosion and high temperature oxidation had corrosion resistance in boiling sulfuric acid. Bilayer structure of silica scale produced by high temperature oxidation was not affected by sulfate corrosion. (S.Y.).
The thermodynamics of protonation and europium(III) complex formation with substituted methane diphosphonic acids have been reported recently. These ligands form strong complexes with europium in moderately acidic solutions ((H{sup +}) {ge} 0.1 M), conditions not conducive to complexation by most carboxylate and aminopolycarboxylate ligands. A correlation of log {beta} vs pK{sub a} values for phosphonate and carboxylate ligands is used to explore the effect of ligand structure on complex stability. 5 refs., 1 fig.
Carbalkoxylation of vinyl electrophiles was investigated using platinum complexes. This reaction occurs in two steps: (a) carbonyl insertion of {sigma}-vinyl Pt(II) halides and (b) alcoholysis of vinylic acyl Pt(II) complexes. Alcoholysis of vinylic acyl Pt(II) triflate complexes is investigated kinetically. Vinylic acyl Pt(II) complexes were isolated and characterized. 51 refs., 5 figs., 6 tabs.
The formation and stability constants of the [sup(99m)Tc]PM tetracycline have been investigated by the potentiometric method. The pK value of the complex formed was measured as pK = 5.49 +- 0.19. The spectrophotometric study has been performed on the formation of a complex of Sn(II) and TcO"4"- in the presence of PM Tetracycline. This study shows that Sn(II) forms with PMT a complex at a mole ratio of 1:1. The molar extinction coefficients of the Sn-PMT and [_9_9Tc]PMT complexes have been measured. (author).
Al, Ga and In complexing with methylthymol blue (H_6R) purified by gel filtration is studied. in the case of metal excess complexes with the ratio of components M:H_6R=2:1 with #lambda#=587(Al), 590(Ga) and 593 nm(In) appear. In the case of reacting agent excess complexes with the ratio of component 1:1 with #lambda#_m_a_x=480-490 (Al) and 480 nm(Ga, In) appear. The mechanism of complexing reactions is studied. Molar extinction coefficients and stability constants are calculated.
Cathodic arc deposition is an established and industrially applied technique for the formation of nitrides (e.g. TiN); it can also be used for metal oxide thin film formation. A cathodic arc plasma source with the desired cathode material is operated in an oxygen atmosphere of appropriate pressure, and metal oxides of various stoichiometric composition can be formed on different substrates. We report here on a series of experiments on metal oxide formation by cathodic arc deposition for different applications. Black copper oxide has been deposited on accelerator components to increase the radiative heat transfer between the parts. Various metal oxides such as tungsten oxide, niobium oxide, nickel oxide and vanadium oxide have been deposited on ITO glass to form electrochromic films for window ...
With an objective to learn reactivity of coal at its surface, surfaces of oxidized coal samples were investigated. Miike coal was oxidized by using {sup 18}O2 in a closed loop system. As the reaction progresses, proportion of CO2 including isotopes increased rapidly as a result of oxidation of CO sites existing in the coal and the newly generated C{sup 18}O sites. The oxidizing reaction progressed via oxygen adsorbing sites generated near the surface, and oxygen containing groups. An FT-IR analysis estimated the depth of the oxidized layer to be 10{mu}m or less from particle surface. The oxidized coal was pulverized to see its surface condition. Functional groups introduced by the oxidation enter into the vicinity of the surface in a form to desorb as CO. CO2 is trapped in inner pores. The coal surface was observed by using an atomic force ...
Zirconium and particularly Zr-2.5wt%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 pro...
In recent years, the influences of acid rain such as the acidification of lake water, on bio-system by the heavy metals from effluent of soils with acid rain and also on the structural materials of buildings are seriously discussed. Sulfur and nitrogen that are contained in fossil fuels are released into the atmosphere by the fuel combustion as their oxides dissolve in rain drops as sulfite and nitrous ions, where they are further oxidized into sulfate and nitrate ions These ions lower the pH of rain water resulting so-called acid rain. Therefore, it is important to accurately determine these ions in rain water for the investigation of reality of acid rain. However, it is not easy to accurately determine these ions, especially for sulfite ions in rain water, since they are quickly oxidized by the catalytic action of metallic ions such as ferric and manganous ions. And light, temperature, pH of solution and also species and ...
The oxide colloidal route, developed in the laboratory for mono-metallic catalysts, consists in preparing a metallic oxide hydro-sol which leads to the supported catalyst after deposition onto a support and an activation stage. In this work, this method has been adapted to the preparation of alumina supported bimetallic Pd-Sn catalysts to determine its interest for the control of the properties of the bimetallic phase (size, composition and structure). In the preliminary study concerning tin oxide sols, SnO{sub 2} (size=2,3 nm) and Sn{sub 6}O{sub 4}(OH){sub 4} (size = 25 nm) nano-particles were synthesized by neutralization respectively for tin(IV) and tin(H). The control through the pH of the aggregation of the PdO and SnO{sub 2} particles revealed that increasing oxide solubility promotes integral re-dispersion of the oxide particles. To synthesize oxide ...
The construction materials used in coolant systems in nuclear power plants become covered with oxide films as a result of exposure to the aqueous environment. The susceptibility of the materials to different forms of corrosion, as well as the extent of the incorporation of radioactive species on the surfaces of the primary circuit, are greatly influenced by the physical and chemical properties of these oxide films. The composition and characteristics of the oxide films in turn depend on the applied water chemistry. This work was undertaken in order to collect and evaluate the present views on the structure and behaviour of oxide films formed on iron- and nickel-based materials in aqueous environments. This survey should serve to recognise the areas in which more understanding and research effort is needed. The review begins with a discussion on the bulk oxides of iron, nickel and ...
The formation of thin SiO_2 layers on silicon and metal silicides was studied by phase- and thickness measurements with Rutherford back-scattering of 2 MeV alfa particles. Thermal oxidation was done in steam and dry oxygen at temperatures between 750 degrees Celsius and 1 100 degrees Celsius, while SiO_2 formation at room temperature was carried out by anodic oxidation. The study of silicon oxidation was done on Si<100>, Si<111> and amorphous silicon substrates. Thermal oxidation of CoSi_2, CrSi_2, NiSi_2, PtSi and TiSi_2 was investigated. The oxidation rates of the silicides were found to be much higher than for silicon. The oxidation process is also diffusion-limited with a higher oxidation rate for steam as compared to dry oxygen. The silicide layers were found to stay intact during thermal oxidation. A ...
The morphological development of oxide scales formed on a low Al substituted #beta#-sialon (z=0.2) oxidised for time periods up to 1024h at 1350 C is discussed in relation to oxidation kinetics. The oxidation process is observed to be accompanied by changes in both the phase assemblage of the external layers and their morphology. Thus as the time of oxidation increases beyond 64h the cristobalite-#beta#-yttrium disilicate phase assemblage changes to cristobalite plus #beta#- and #gamma#-yttrium disilicate. In addition to the changes observed for the surface layers, differences are observed in the morphologies of the polished cross-sections. These changes are consistent with an order of magnitude decrease in oxidation rate. (orig.).
Regularities of deformation-induced dissolution of a surface layer of iron oxides in matrixes of iron-based alloys with bcc and fcc lattices have been studied by the methods of M?ssbauer spectroscopy, transmission electron microscopy, and X-ray diffraction. A method of producing iron alloys strengthened by dispersed oxide nanoparticles and alloyed with elements possessing a high affinity to oxygen (titanium and yttrium) has been proposed, which implies a dynamic dissolution of a surface layer of iron oxides upon strong cold deformation and a precipitation of secondary yttrium and titanium nanooxides upon a subsequent high-temperature sintering of mechanically alloyed powders. There has been demonstrated a possibility of oxide strengthening of pure iron upon its interaction with air without...
MCrAlY coatings are widely used on hot section components of gas turbines to provide hot corrosion and/or oxidation protection by formation of an oxide layer on the surface. As the protective oxide scale exfoliates during service, aluminum from the coating diffuses outward for reformation of the protective scale. Aluminum may also diffuse inward due to the differences in composition between the coating and the substrate. Thus, the coatings degrade due to oxidation, oxide scale spallation, and inward and outward diffusion of aluminum. Service life of these coatings is controlled by the aluminum content in the coating, operating temperature and start- shutdown cycles. In-service degradation of CoCrAlY and CoNiCrAlY coatings is presented. A procedure to predict the remaining service life of coatings under oxidizing conditions is discussed. (orig.) 12 refs.
The phosphate complexation of Np(V) is investigated in the pH range from 6.4 to 10.0 in 0.1 M NaClO_4 at 22#+-#2 C by absorption spectroscopy. The formation of two phosphate complexes is confirmed by spectroscopic speciation: NpO_2HPO"-_4 at 988.8 nm and NpO_2PO"2"-_4 at 993.6 nm with molar extinction coefficients of 251#+-#8 and 201#+-#11 1/mol cm, respectively. The complexation constants are determined to be log #beta# = 2.54#+-#0.02 for NpO_2HPO"-_4 and log #beta# = 6.33#+-#0.08 for NpO_2PO"2"-_4. The competition of the phosphate complexation with the carbonate complexation is demonstrated by speciation calculation under different geochemical conditions. (orig.).
Complex fluids have long posed a significant challenge in our ability to characterize and model fluid properties. Here, we consider complex fluids to be mixtures with many components that can differ significantly in polarity and polarizability. The penultimate complex fluid is crude oil, although many other fluids such as finished fuels are also highly complex. We have recently introduced a measurement strategy that can simplify these efforts and provides the added potential of linking chemical composition (i.e. analytical) information with physical property information. In addition to chemical characterization, the approach provides the ability to calculate thermodynamic and transport properties for such complex heterogeneous streams. The technique is based on the advanced distillation cu...
A variable gene delivery system has been developed based on conjugating chitosan to biotin through a functionalized poly(ethylene glycol) (PEG) spacer, which can be used to further bind different molecules on the outer layer of a polymer/DNA complex by streptavidin (SA)-biotin linkage. In this study, TAT-conjugated SA was used as the model molecule to prove the conjugation function of the prepared complex. In addition, low-molecular-weight poly(ethyleneimine) (PEI) was added into the polymer/DNA complex to increase the transfection efficiency. The results of the luciferase assay show that the transfection efficiency of the prepared complex was significantly correlated with the amount of PEI and was further enhanced when TAT was conjugated to the complex by SA-biotin linkage. Considered to have negligible cytotoxic effects, the variable gene delivery complex ...
NO{sub x} compounds, specifically NO and NO{sub 2}, are pollutants and potent greenhouse gases. Compact and inexpensive NO{sub x} sensors are necessary in the next generation of diesel (CIDI) automobiles to meet government emission requirements and enable the more rapid introduction of more efficient, higher fuel economy CIDI vehicles. Because the need for a NO{sub x} sensor is recent and the performance requirements are extremely challenging, most are still in the development phase. Currently, there is only one type of NO{sub x} sensor that is sold commercially, and it seems unlikely to meet more stringent future emission requirements. Automotive exhaust sensor development has focused on solid-state electrochemical technology, which has proven to be robust for in-situ operation in harsh, high-temperature environments (e.g., the oxygen stoichiometric sensor). Solid-state sensors typically rely on yttria-stabilized zirconia (YSZ) as the oxygen-ion conducting electrolyte and then target ...
Ruthenium is one of the fission products in the reprocessing of irradiated fuels that requires a specific processing management. Its elimination, upstream by the PUREX process, has been considered. A process, called electro-volatilization, which take advantage of the RuO{sub 4} volatility, has been optimised in the present study. It consists in a continuous electrolysis of ruthenium solutions in order to generate RuO{sub 4} species that is volatilized and easily trapped. This process goes to satisfying ruthenium elimination yields with RuNO(NO{sub 3}){sub 3}(H{sub 2}O){sub 2} synthetic solutions but not with fuel dissolution solutions. Consequently, this work consisted in the speciation studies of dissolved ruthenium species were carried out by simulating fuel solutions produced by hot acid attack of several ruthenium compounds (Ru(0), RuO{sub 2},xH{sub 2}O, polymetallic alloy). In parallel with dissolution kinetic studies, the determination of dissolved species was performed using ...
Determination of the specific surface of uranium oxides: UO_2 and U_3O_8 using a simplified equation derived from the Brunauer, Emmett and Teller theory. The method is suitable for samples having a surface between 6 to 50 m"2.
PurposeHeavy metals and other forms of oxidative stress have been implicated as key factors in the formation of age-related cataract in humans. Metallothioneins are...Full Text Available
Reactive oxygen species (ROS), inevitable byproducts of aerobic metabolism, are known to cause oxidative damage to cells and molecules. This, in turn, is widely accepted as a pivotal determinant of...Full Text Available
Altered structure, and hence function, of cellular macromolecules caused by oxidation can contribute to loss of physiological function with age. Here, we tested whether the lifespan of bats, which generally...Full Text Available
The influence of surface oxides of variable composition and nonstoichiometry formed at high temperatures in air on the general corrosion resistance of ferritic chromium steel type 08H17T (Fe-17Cr-1Ti) in weak sulfuric acid has been studied. Anodic passive films formed on steel with different pretreatments have also been examined. The surface oxide of nearly stoichiometric composition formed at 300 C provides for the passive state of steel in sulfuric acid despite its depletion by chromium when compared with that for nonstoichiometric Cr-enriched oxide formed at 600 C. The dissolution and transformation of nonstoichiometric thermal surface oxide in sulfuric acid appear to take place through defect sites, {minus}Fe{sup 2+} ions, and oxygen vacancies of the n-type conductor. The passive film formed on the nonstoichiometric oxide film, which had been produced at 600 C, was found to be ...
BackgroundFree nitric oxide (NO) reacts with sulphydryl residues to form S-nitrosothiols, which act as NO reservoirs. We sought to determine whether thiol-preserving...Full Text Available
The purpose of this study was to synthesize biocompatible polyvinylpyrrolidone (PVP)-coated iron oxide (PVP-IO) nanoparticles and to evaluate their efficacy as a magnetic resonance imaging (MRI)...Full Text Available
A catalytic process for the oxidation of sulfur-containing gases , E.G., sulfur dioxide and simultaneous production of sulfuric acid wherein a sulfur-containing gas is reacted with an oxygencontaining gas in the presence of a catalyst comprising an iron group metal on a solid support comprising a zeolite in a silicaalumina matrix.
4-Hydroxynonenal (HNE), a major electrophilic product of lipid peroxidation, is regarded as both a marker of oxidative stress and a mediator of oxidative damage. At subtoxic concentrations,...Full Text Available
The gelation kinetics of an in situ gelable hydrogel formulated from oxidized dextran (Odex) and N-carboxyethyl chitosan (CEC) were investigated rheologically. Both Schiff base...Full Text Available
It is shown analytically and experimentally that thermally stimulated current (TSC) measurements at negative bias incompletely describe oxide-trap charge in SIMOX and bipolar base oxides irradiated at 0 V. Positive-bias TSC is also required.
Rheological properties of moderately concentrated solutions of cellulose in methylmorpholine N-oxide-dimethylformamide mixtures containing hydrophilic montmorillonite nanoparticles were studied. Film composite materials were prepared, and their physicomechanical properties and structural organization were studied.
We report the use of cysteine-substituted mutants in conjunction with in situ oxidation to determine the physical proximity of a pair of engineered cysteines in the pore region of the voltage-gated...Full Text Available
A series of in situ gelable hydrogels were prepared from oxidized dextran (Odex) and N-carboxyethyl chitosan (CEC) without any extraneous crosslinking agent. The gelation readily...Full Text Available
A multidisciplinary approach was used to study the effects of pollution from a marine fish farm on nitrification rates and on the community structure of ammonia-oxidizing bacteria in the underlying...Full Text Available
This study was conducted to determine by gas chromatography (GC) and mass spectrometry (MS) the identity and the quantity of volatile N products produced during the helium-purged in vivo...Full Text Available
The OH-initiated photo-oxidation of n-butane was used as a source of 1- and 2-butoxy radicals. Reactions producing ketones and other organic compounds are explained. Rates of photolysis were determined and are discussed.
Because copper catalyzes the conversion of H2O2 to hydroxyl radicals in vitro, it has been proposed that oxidative DNA damage may be an important component of copper toxicity....Full Text Available
Oxidative stress has been implicated in the etiology of age-related muscle loss (sarcopenia). However, the underlying mechanisms by which oxidative stress contributes to sarcopenia have not been thoroughly...Full Text Available
The authors investigate the possibility of the direct heterogeneous catalytic synthesis of ethylbenzoate from benzonitrile. The catalysts tested were oxides of aluminium, titanium, and vanadium. The main conversion product detected chromatographically was ethylbenzoate; benzaldehyde, benzamide, and benzanilide were also identified. Aluminium oxide was found to be the most effective catalyst.
Neurons in the hippocampal CA1 region are particularly sensitive to oxidative stress (OS), whereas those in CA3 are resistant. To uncover mechanisms for selective CA1 vulnerability to OS, we...Full Text Available
The neuronal nitric oxide synthase gene (NOS1) is located at 12q24, a susceptibility region for schizophrenia, and produces nitric oxide (NO). NO has been reported to play important...Full Text Available
Quantitative probing of heterogeneous regions in muscle is feasible with phosphorus-31 magnetic resonance spectroscopy because of the differentiation of metabolic patterns of glycolytic and oxidative...Full Text Available
Thermophilic propionate-oxidizing, proton-reducing bacteria were enriched from the granular methanogenic sludge of a bench-scale upflow anaerobic sludge bed reactor operated at 55°C with a mixture...Full Text Available
Bacterial nitric oxide synthases (bNOS) are present in many Gram-positive species and have been demonstrated to synthesize NO from arginine in vitro and in vivo. However, the physiological role...Full Text Available
BackgroundClara cell protein (CC16), the main secretory product of bronchiolar Clara cells, plays an important protective role in the respiratory tract against oxidative stress and...Full Text Available
The oxidation conditions were investigated for obtaining a higher productivity in the production of high strength carbon fiber from polyacrylonitrile (PAN). The effect of incorporation of 2 % comonomer such as methyl acrylate (MA), acrylate containing carboxylate (SA), acrylamide (AAm), and hydroxyethyl acrylate (HEA) on the oxidation conditions was also investigated. The measurement of DSC and bonded oxygen content revealed that the most effective comonomer for promoting the cyclization of nitril group and the bonding of oxygen was found to be SA, and the second best was AAm. The measurement of tensile strength of carbon fiber showed that the copolymer of SA, HEA, and MA gave a high strength fiber. It took a long time to oxidize the carbon fiber when it was oxidized at a temperature on which double layer structure was not formed. To shorten the production time, a method of combining the upper limit ...
BackgroundTrichloroethylene (TCE) may induce oxidative stress which generates free radicals and alters antioxidants or oxygen-free radical scavenging enzymes.MethodsTwenty...Full Text Available
Systemic administration of lipopolysaccharide (LPS), which causes endotoxemia and systemic inflammation, has been reported to induce expression of the gene for type II inducible nitric oxide synthase...Full Text Available
Three nucleic acid probes, two for autotrophic ammonia-oxidizing bacteria of the beta subdivision of the class Proteobacteria and one for alpha subdivision nitrite-oxidizing bacteria, were developed...Full Text Available
The electrochemical behavior of lanthanide oxides in molten alkaline chloride media is of great concern in pyrochemical processes for advanced nuclear fuel cycle. We have studied the solubilities of various lanthanide oxides in LiCl-KCl eutectic melt. In general, lanthanide oxides appeared to be insoluble/sparingly soluble in LiCl-KCl eutectic at 723 K. However, europium oxide exhibited an abnormal behavior in solubility and redox chemistry. The solubility of europium oxide was measured to be 1-2 order of magnitude higher than those of other lanthanide oxides. This abnormal solubility may be attributable to different electrochemical behavior of europium in the same experimental conditions. Most lanthanides ion exists as trivalent oxidation states. However, we observed divalent europium dissolved in LiCl-KCl molten salt by applying electron ...
1. The effect on rat liver peroxisomal beta-oxidation of feeding diets containing various amounts of dietary oils was investigated. With increasing amounts (5-25%, w/w) of soya-bean oil an apparent,...Full Text Available
This patent describes a method comprising applying a passivation layer of CaF{sub 2} to the surface of a superconductive ceramic oxide by evaporation. The CaF{sub 2} layer is effective to passivate the oxide surface without disrupting the superconductive properties.
Suspensions of denitrifying cells of Pseudomonas perfectomarinus reduced nitrate and nitrate as expected to dinitrogen; but, in the presence of acetylene, nitrous oxide accumulated when nitrate or nitrate...Full Text Available
There is increasing evidence of a biochemical link between lipid oxidation and bone metabolism. Paraoxonase 1 (PON1) prevents the oxidation of low-density lipoprotein (LDL) and metabolizes biologically...Full Text Available
BackgroundArsenic (As) exposure during pregnancy induces oxidative stress and increases the risk of fetal loss and low birth weight.ObjectivesIn...Full Text Available
Anionic peroxidase from tomato (Lycopersicon esculentum) fruit oxidized indoleacetic acid (IAA) slowly in the presence of Mn2+ and dichlorophenol in acetate buffers. The...Full Text Available
The aim of the present study was to evaluate the ameliorative potential of quercetin (QC) against paracetamol (PCM)-induced oxidative stress and biochemical alterations in mice blood. A total of 36...Full Text Available
Evolution of nitrogen oxides (NO(x), primarily as nitric oxide) from soybean (Glycine max [L.] Merr.) leaves during purged in vivo nitrate reductase assays...Full Text Available
Increased oxidative stress with elevated levels of reactive oxygen and nitrogen species (ROS/RNS) plays an important role in the pathophysiology of many disease states. Increased ROS/RNS can...Full Text Available
Tuberous Sclerosis Complex (TSC) is a neurogenetic disorder caused by loss-of-function mutations in either the TSC1 or TSC2 genes and frequently results in...Full Text Available
The mini-chromosome maintenance proteins Mcm2–7 are essential for DNA replication. They are loaded onto replication origins during G1 phase of the cell cycle to form a pre-replication complex...Full Text Available
The effects of bovine α-globulin (BAG), bovine-ribonuclease serum albumin (BSA-RNase) and polyribonuclease (poly-RNase) complexes on the primary response of rodents to sheep erythrocytes have...Full Text Available
We have developed a method to extract and separate phytochelatins (PCs)—metal(loid) complexes using parallel metal(loid)-specific (inductively coupled plasma-mass spectrometry) and organic-specific...Full Text Available
Genetic defects in the dystrophin-associated protein complex (DAPC) are responsible for a variety of pathological conditions including muscular dystrophy, cardiomyopathy, and vasospasm. Conserved DAPC...Full Text Available
Platinum(II) complexes (1-4) with bidentate N,Nprime-ligands, O,Oprime-dialkyl esters (alkyl = ethyl, n-propyl, n-butyl and n-pentyl), of (S,S)-ethylenediamine-N,Nprime-di-2-(4-methyl)pentanoic acid were synthesized and characterized by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. DFT calculations were performed for the complexes and it was found that only one diastereoisomer could be formed. Cytotoxic activity of complexes 1-4 was determined against chronic lymphocytic leukemia cells (CLL) and compared to the activity of ligand precursors L12HCl-L42HCl and corresponding palladium(II) complexes, [PdCl2L] (L = L1-L4). The complexes were found to exhibit significantly higher antitumor activities than cisplatin on CLL cells. Cytotoxic effect of platinum(II) complexes on CLL cel...
We ran a comparative analysis of all patients for whom a positive culture of Mycobacterium tuberculosis complex was available between April 2004 and October 2005 and whose HIV serology...Full Text Available
We show here sodium ion cycling between complex I from Klebsiella pneumoniae and the F1F0 ATP synthase from Ilyobacter tartaricus in a reconstituted...Full Text Available
A general method is described to sequester peptides containing azides from complex peptide mixtures, aimed at facilitating mass spectrometric analysis to study different aspects of proteome...Full Text Available
Yeast Sir2 deacetylase is a component of the silent information regulator (SIR) complex encompassing Sir2/Sir3/Sir4. Sir2 is recruited to telomeres through Rap1, and this complex spreads into subtelomeric...Full Text Available
Resonance Raman spectra are reported for the organometallic phenyl-FeIII complexes of horse heart myoglobin. We observed the resonance enhancement of the ring vibrational modes of the bound phenyl group....Full Text Available
We use high-density single nucleotide polymorphism (SNP) genotyping microarrays to demonstrate the ability to accurately and robustly determine whether individuals are in a complex genomic DNA mixture....Full Text Available
The main aim of the present study was to evaluate potential of ternary complexation (comprising of drug, cyclodextrin and polymer) as an approach for taste masking. For this purpose famotidine with...Full Text Available
Rapamycin inhibits the mTOR (target of rapamycin) pathway and extends lifespan in multiple species. The tuberous sclerosis complex (TSC) protein is a negative regulator of mTOR. In humans, loss of the...Full Text Available
The article gives a brief description of the state of the nuclear power engineering in Ukraine and in the world as of today. There are basic organizational and practical actions on scientific and technical maintenance of the Ukraine nuclear power complex presented in the article.
The number of nuclear pore complexes (NPCs) in individual nuclei of the yeast Saccharomyces cerevisiae was determined by computer-aided reconstruction of entire nuclei from electron...Full Text Available
Endosomal sorting complexes required for transport (ESCRTs) are heteromeric protein complexes required for multivesicular body (MVB) morphogenesis. ESCRTs I, II, III and III-associated are ubiquitous...Full Text Available
A process for the recovery of nitrilotriacetic acid values from solutions containing polyvalent metal complexes of nitrilotriacetic and the decomposition products thereof is described, the process being characterized by the addition to such solutions of sufficient strong acid to dissociate the complex under conditions to precipitate the nitrilotriacetic acid.
Photosynthetic antenna complexes capture and concentrate solar radiation by transferring the excitation to the reaction center that stores energy from the photon in chemical bonds. This process occurs...Full Text Available
Sheep choroid plexus cells infected with visna virus produce intracytoplasmic viral ribonucleoprotein complexes with sedimentation values of 120S to 200S and buoyant densities of 1.29 to 1.32 g/cm3....Full Text Available
The bulky octahedral complex, Rh(bpy)2chrysi3+ (chrysi = 5, 6- chrysenequinone diimine), binds single base mismatches in a DNA duplex with micromolar binding affinities...Full Text Available
Major histocompatibility complex (MHC) genes are highly polymorphic components of the vertebrate immune system, which play a key role in pathogen resistance. MHC genes may also function as odour-related...Full Text Available
The Carassius auratus complex in natural populations includes diploid triploid and polyploidy individuals. Diploid individuals belong to the species Carassius auratus...Full Text Available
The genetic architecture of complex traits underlying physiology and disease in most organisms remains elusive. We still know little about the number of genes that underlie these traits, the magnitude...Full Text Available
The presence of DNA-anti-DNA complexes in sera from patients with systemic lupus erythematosus (SLE) was investigated by two new radioimmunoassays (RIA) developed for this purpose and by measuring the...Full Text Available
Metazoan life cycles can be complex in different ways. A number of diverse phenotypes and reproductive events can sequentially occur along the cycle, and at certain stages a variety of developmental...Full Text Available
Adopting the approach taken with New Caledonian crows (Corvus moneduloides), we present evidence of design complexity in one of the termite-fishing tools of chimpanzees (Pan...Full Text Available
Designer cellulosomes are precision-engineered multienzyme complexes in which the molecular architecture and enzyme content are exquisitely controlled. This system was used to examine enzyme cooperation...Full Text Available
We report a case of a female patient who was operated at the third relapse of an atrial myxoma caused by Carney complex. The difficult operation was performed without any complications despite extensive...Full Text Available
A new /sup 99m/Tc-phosphine-isocyanide complex with the general structure (/sup 99m/Tc (DEPE)/sub 2/(CNR)/sub 2/)/sup +/ has been synthesised and tested in animals and one human. In three animal species (rat, rabbit, dog), the complex is an efficient myocardial imaging agent, while in humans it remains in the blood pool. The complex is 100% protein bound in animals and humans, but whereas in humans it is attached to a 51.5 kdalton protein (probably prealbumin), in rabbits it appears to be bound to a larger macromolecule (M.W.>100 kdalton). The efficiency of the complex for blood pool labelling was tested in a human volunteer and compared with the standard in vivo red cell labelling technique with stannous pyrophosphate. A satisfactory radionuclide angiogram could be performed with less than 370 MBq of the complex. The count rate for the complex (cps/MBq) was ...
Endogenous immune complexes present in sera from 10 different patients with systemic lupus erythematosus (SLE) in an active phase were allowed to bind to Raji cells; the ability of intact complement...Full Text Available
BackgroundThe genomic organisation of the Major Histocompatibility Complex (MHC) varies greatly between different vertebrates. In mammals, the classical MHC consists of a large number...Full Text Available
The function of the hyolingual complex in three odontocete species was investigated to compare adaptations of divergent feeding strategies, suction and ram feeding. Pygmy and dwarf sperm whales, members...Full Text Available
MOM22 is a component of the protein import complex of the mitochondrial outer membrane of Neurospora crassa. Using the newly developed procedure of 'sheltered disruption', we created a heterokaryotic...Full Text Available
A detection theory is developed for point-contact metal-oxide-metal (MOM) systems. A system with heterogeneous oxide strongly bonded to the substrate is considered. It is shown that the form of the functional connection between the barrier heights and the ultimate compressive strength of the oxide has no substantial influence on the voltage-current characteristics of the system. Quantitative analysis indicates that a MOM system can behave as a tunnel diode and as a diode with a Schottky barrier. The model permits the determination of the optimum construction of long-life detectors based on MOM point-contacts.-
This paper reports on hydrolysis of 10 metal salt aqueous solutions of 6 metal oxides that was conducted in supercritical water. Continuous and rapid production of metal oxide fine particles was achieved by mixing a metal salt aqueous solution with preheated water fed from another line. The reaction time required was less than 2 min. Particle size, morphology, and crystal structure of the obtained metal (hydrous) oxides were examined. Particle size (20 to 600 nm) was different among the system but the size range was relatively narrow in all the cases.
Partial oxidation of 2-propanol was carried out on AB{sub 1-x}B`{sub x}O{sub 3} (A=Ba, B=Pb, Ce, Ti; B`=Bi, Sb and Cu) type perovskite oxides. Acetone was the major product observed on all the catalysts. All the catalysts underwent partial reduction during the reaction depending on the composition of the reactant, nature of the B site cation and the extent of substitution at B site. The catalytic activity has been correlated with the reducibility of the perovskite oxides determined from Temperature Programmed Reduction (TPR) studies. (orig.)
Green River oil shale was air oxidized at subretorting temperatures. Off gases consisting of nitrogen, oxygen, carbon monoxide, carbon dioxide, and water were monitored and quantitatively determined. A mathematical model of the oxidation reactions based on a shrinking core model has been developed. This model incorporates the chemical reaction of oxygen and the organic material in the oil shale as well as the diffusivity of the oxygen into the shale particle. Diffusivity appears to be rate limiting for the oxidation. Arrhenius type equations, which include a term for oil shale grade, have been derived for both the chemical reaction and the diffusivity.
... Title : Effect of Yttrium on the Microstructure of Titanium Alloys,. ... The yttrium was added in the melting stage as an oxide or in the elemental form. ...
Objective of the project is characterization of electrode reactions in molten salt by using metal oxides and silica-based electrode. The scope of project are characterization of metal oxide properties in molten salt and miniaturization of 3-electrode electrochemical test cell. Electrochemical micro-cell for actinide-LiCl-KCl molten salt was newly designed. Electroless and electrochemical deposition technique was applied to Mo coating on quartz tube. From the design of electrode and 3-electrode electrochemical cell suitable for the tests in molten salt electrolyte, so it is anticipated to get the information on the electrochemical behavior of metallic electrode in molten salt and to secure the information on oxidation/reduction behavior of actinide
Measurements were completed on the solubility of cupric and cuprous oxides in liquid water and steam at controlled pH conditions from 25 to 400 C (77 to 752 F). The results of this study have been combined with those reported from this laboratory in two previous EPRI reports to provide a complete description of the solubility of these oxides and the speciation of copper dissolved in liquid water and steam as a function of oxidation state, temperature, pH, and in the case of steam, pressure. These constitute the first set of reliable data for cuprous oxide solubility over this range of conditions. For the more intensively studied CuO case, agreement was found between our results and those of previous studies of its solubility in steam, whereas only partial agreement was evident for its solubility in liquid water. For both oxides this disagreement often amounted to orders of ...
Full text of publication follows: Large-scale problems such as nuclear waste disposal are increasingly recognized to be interconnected to small scale-mechanisms. Thus, synchrotron-based high-resolution analytical X-ray probes become important tools for exploring the micro-scale chemical reactivity of heterogeneous barrier materials used in nuclear waste repositories. In this study the layout of the micro-XAS beamline at the Swiss Light Source (SLS) will be presented. The beamline is optimized towards micro beam experiments ({approx}1 x 1 {mu}m{sup 2}) in the hard-X-ray regime (4 - {approx}22 keV) and allows to combine micro X-ray fluorescence (micro-XRF), micro X-ray absorption spectroscopy (micro- XAS), and micro X-ray diffraction (micro-XRD) investigations with radioactive samples. Furthermore, the potential of micro-XRF/XAS/XRD for acquiring spatially resolved molecular level information on the speciation and structural coordination environment of radionuclides in heterogeneous ...
This paper is to report a case of multi-ruptured complex pseudoaneurysm confirmed by three-dimensional DSA. Under three-dimensional DSA guidance, the thrombin was injected into lumens in the attempt to cure the pseudoaneurysm. As the result was unsatisfactory, fibrin sealant was used to inject into the lumens again, and good curative effect was obtained. In clinical interventional practice, the incidence of pseudoaneurysm has been steadily increasing and the lesions have become more and more complex. In this paper the authors have discussed the diagnostic and therapeutic methods of complex pseudoaneurysm in order to provide clinical physicians with useful information. (authors)
The absorption, emission and magnetic circular dichroism spectra of the anionic complex (Cp_3Pr. NCS)"- were measured at room and low temperatures. On the basis of these spectra the electronic structure in the f-f range could be derived. The parameters of an empirical Hamiltonian were fitted to the experimentally determined crystal field splitting pattern. Compared with the previously examined neutral Cp_3 Pr.X complexes the quadratic crystal field parameter B_0"2 is considerably reduced.
The first preparation and characterization of the platinum (II) complexes containing five phosphorus ligands are reported herein. The complexes are represented by the formulae (Pt(PP/sub 3/)(P(OR)/sub 3/)Cl/sub 2/, where R = Me or Et, and (Pt(PP/sub 3/)(PEt/sub 3/))Cl/sub 2/. The /sup 31/P spectra of the complexes are presented. 10 references, 2 tables.
Three novel inosine-based dinuclear platinum complexes have been synthesized via a solid-phase strategy. In these compounds, the metal is linked both to the N-7 of the purine nucleus and to the terminal amine group of a hexylamine side chain installed on N-1. Cis- or trans- diamine as well as ethylenediamine ligands are coordinated to platinum along with a chloride. The synthesised complexes were tested against four different human tumor cell lines. One of these complexes proved to be more cytotoxic than cisplatin against the MCF7 cancer cell line in a short-term exposure assay.
... interactive surfaces and interfaces, and 3) the more complex a ... carbonate or calcium phosphate with a thin interface ... diameter) for nerve prosthesis. ...
The phase transition is a performance measure of the sparsity-undersampling tradeoff in compressed sensing (CS). This letter reports, for the first time, the existence of an exact phase transition for the $\\ell_1$ minimization approach to the complex valued CS problem. This discovery is not only a complementary result to the known phase transition of the real valued CS but also shows considerable superiority of the phase transition of complex valued CS over that of the real valued CS. The results are obtained by extending the recently developed ONE-L1 algorithms to complex valued CS and applying their optimal and iterative solutions to empirically evaluate the phase transition.
This Waste Management Plan functions as a management and planning tool for managing waste streams generated as a result of operations at the Idaho CERCLA Disposal Facility (ICDF) Complex. The waste management activities described in this plan support the selected remedy presented in the Waste Area Group 3, Operable Unit 3-13 Final Record of Decision for the operation of the Idaho CERCLA Disposal Facility Complex. This plan identifies the types of waste that are anticipated during operations at the Idaho CERCLA Disposal Facility Complex. In addition, this plan presents management strategies and disposition for these anticipated waste streams.
Thermal wet oxidations of GaP and Al{sub 0.4}Ga{sub 0.6}P at 650 degree sign C for various times have been performed. Comparisons are made on oxidation rates and post oxidation morphology. Transmission electron microscopy shows that when oxidizing GaP, polycrystalline monoclinic GaPO{sub 4}{center_dot}2H{sub 2}O forms without noticeable loss of phosphorus. Oxidation for 6 h or more leads to poor morphology resulting in cracks and detachment. A thickness expansion of about 2.5-3 times is noticed as a result of oxidation. In contrast, oxidized Al{sub 0.4}Ga{sub 0.6}P exhibits much better morphology without cracks or detachment from the substrate. The oxide has an almost amorphous-like microstructure. The oxidation process shows typical diffusion-limited reaction at long anneals. Preliminary work on the ...
This articles deals with an approach that has given some key information about the mechanisms of the liquid phase oxidation of butane to acetic acid. This procedure has been developed over the last 34 years; however, much of what will be discussed represents a synthesis of previous insights. Many of the observations are relatively recent and have not been previously published. In principle, this approach should be applicable to many oxidation processes. (orig.)
The behaviour of an elastomeric seal for vehicle brake Tandem master cylinder is measured and analyzed in temperature and brake fluids changed. Working conditions are simulated for different piston rod velocity and cylinder supply pressure, in temperature rising, brakefluid boundary and Nanoaluminum oxide brakefluid oxide brakefluid lubrication. The result shows that Nanoaluminum oxide brakefluid with its ball shape can highly reduce friction coefficient to avoid seal excessive wear and reduce slick slip in brake applications.
The application of kinetic probes that allow one to determine relative reactivities of biologically relevant substrates with oxidizing intermediates in the Fenton reagent (H2O2 plus Fe2+ in acidic aqueous...Full Text Available
A two-step purification protocol was used in an attempt to separate the constitutive NAD(P)H-nitrate reductase [NAD(P)H-NR, pH 6.5; EC 1.6.6.2] activity from the nitric oxide and nitrogen dioxide (NO(x))...Full Text Available
The authors have determined quantitative characteristics for oxide films forming on (111) surfaces of cadmium telluride single crystals on anodic oxidation in 0.1 M KOH: the constants in the Guenterschulze-Betz equation and the film growth constant, which is 2.4 nm/V, from which the activation energy for cadmium telluride electrooxidation has been calculated.
The following methods of quartz ceramics alloying were considered: alloying of initial quartz glass; introduction of alloying additive into water slip of quartz glass; porous materials impregnation with salt aqueous solutions and subsequent salt thermal decomposition with formation of stable oxides in pores of ceramics. Oxygen free compounds BN, SiB_4, SiC, Si_3N_4, REM oxides and transition metal oxides were used as alloying additives. Main properties of the materials and compositions obtained are presented.
During electrolysis of a "2"4"8Cm(III) solution in 2M K_2CO_3 at pH=13, partial oxidation of curium to a higher oxidation state, probably Cm(IV), was observed. The absorption spectra of Cm(III) and Cm(IV) in K_2CO_3 solution were recorded and the molar extinction coefficients of main absorption bands of curium were evaluated. (author).
AQ4N (1,4-bis([2-(dimethylamino-N-oxide)ethyl]amino)5,8-dihydroxy- anthracene-9,10-dione) is a novel alkylaminoanthraquinone N-oxide which, on reduction, forms a stable DNA affinic cytotoxic compound...Full Text Available
Consideration is given to results of investigation into thorium complexing with morin (H_2Mor) in extraction systems containing different carboxylic acids as well as different salt background. The obtained data enabled to suggest the method of photometric determination of thorium in the form of Th(HMor)_2Benz_2 different-ligand complex (where Benz-anion of benzilic acid) with 0.25 #mu#g/ml detection limit.
Modern microprocessor-based relays for the protection of the various power system components such as generators, transformers, feeders, and high voltage transmission lines are becoming more sophisticated as increasingly more complex functions and capabilities can be included in the microprocessor. With this increasing complexity, and the increasing complexity of the power system itself, there is even more value in testing the suitability of relaying equipment for the intended applications. This paper reviews the testing philosophy, experience, and capabilities developed at Ontario Hydro over more than 25 years of testing protective relays.
Using the PMR method the interaction of zirconium and hafnium tetrachlorides with tri.tet.butylphenyl ester of 1,2- naphthoquinonediazide (2)-5-sulfonic acid is studied. The formation of MCl/sub 4/xNQD complexes is established, the equilibrium constants and thermodynamic parameters of complexing reaction are determined. The presence of rapid ligand exchange, proceeding according to associative mechanism, is detected. The rate constants and activation energies of the exchange reaction are calculated.
Using the PMR method the interaction of zirconium and hafnium tetrachlorides with tri.tet.butylphenyl ester of 1,2- naphthoquinonediazide (2)-5-sulfonic acid is studied. The formation of MCl_4xNQD complexes is established, the equilibrium constants and thermodynamic parameters of complexing reaction are determined. The presence of rapid ligand exchange, proceeding according to associative mechanism, is detected. The rate constants and activation energies of the exchange reaction are calculated.
Stability constants for uranium-tetracycline complexes were determined by the method of average number of ligands, the method of limiting values, the method of two parameters and the method of weighted least squares. Solvent extraction technique was used to obtain experimental data. (author). 10 refs.; 5 figs.
During the past 3 years, progress was made in elucidating the excited state structures of Pt(diimine)(dithiolate) complexes, while more recent efforts focused on the photochemistry of these complexes and electronic structure of other dithiolate systems. A carbonyl-Ir-maleonitrile dithiolate complex is also studied.
FT-IR spectrum of fulvic acid from wheathered coal of Gongxian is determined using second derivative spectroscopy and the spectroscopic resolution is enhanced. Moreover, FT-IR spectra of the complexes of fulvic acid with Ca"2"+, Ba"2"+, Cu"2"+, Pb"2"+ and UO_2"2"+ under different pH are determined and the nature of the coordination of these complexes is discussed.
The complex formation of astatine(I) cation with diethylene triamine pentaacetic acid (DTPA) and characterization of the complexes were investigated by electromigration in free electrolytes and by gel-chromatography on Sephadex G 25. The conjugation procedure for the production of At-DTPA conjugated polyclonal antibodies is described. (author) 15 refs.; 2 figs.
The complex aspects of high energy physics work are briefly described, and approaches to managing them are discussed. Management of software and data are covered. For managing complexity in experimental physics, the choice of building or buying processor systems is addressed and the issues of compatibility and standardization are discussed. (LEW)
Amphiphilic pincer palladium complexes bearing hydrophilic and hydrophobic side chains on the planar NCN palladium pincer backbone were designed and prepared via the ligand introduction route. The complexes self-assembled under aqueous conditions to form vesicles with bilayer membranes containing palladium species. The catalytic activity of the vesicles in the Miyaura-Michael reaction in water was investigated. PMID:21837316
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO2, PrO2), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two sha...
Coordination of CoCl2 solutions to the silica polyamine composite, WP-1, made with the branched polymer polyethylenimine (PEI) shows irreversible binding resulting from surface oxidation of the Co2+-Co3+. This is not the case for the silica polyamine composite BP-1 made with the linear polymer polyallylamine where reversible binding and no oxidation is observed. These observations suggested that oxidation of the cobalt was related to the greater coordination number available with the branched polyamine relative to the linear polyamine. A study of the kinetics of cobalt binding to WP-1 indicated initial loading of Co2+ at relatively low coordination number followed by desorption of Co2+ leading to oxidation and irreversible binding. Exclusion of oxygen from the composite-cobalt solution mix...
The invention is regeneration and recirculation of nitrogen oxides in the exhaust gas of a nitric acid plant without using any material current and heat energy other than that generated in the process of producing nitric acid. Nitrogen oxide is recovered by at least two adsorbers each containing an acid resistant zeolite molecular sieve and operating in an alternate heat cycle; adsorption occurring at 20-40 degrees C and regeneration at 300-350 degrees C. The hot gas exiting from the oxidation U used in the production of nitric acid is used to regenerate the adsorbers and the nitrogen oxides set free during the said regeneration are introduced into the main feed stream of the nitric acid plant. In the final stage of the regeneration the adsorbers are cooled by rinsing them with exhaust gas or air at a temperature of 20-40 degrees C.
#beta#-sialon ceramics of equal overall compositions but containing amorphous, partly crystalline and almost completely crystalline intergranular phase(s) have been oxidized in oxygen at 1350 deg C for 20 hours. The obtained weight gain curves do not follow the parabolic rate law (#DELTA#W/A_0)"2= k_pt + #beta#. To the extent that crystallization occurs in the oxide scale during the oxidation experiment, the amorphous cross section area through which oxygen most easily diffuses will decrease with time. A brief description of this new rate law is given, and the obtained oxidation curves will be discussed within that framework. 4 refs., 2 tabs., 2 figs.
Chemical modification of poly(?-caprolactone) PCL by oxidation with potassium permanganate in solution was investigated. According to the data obtained from Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance 1H NMR, after the oxidation reactions the PCL chains exhibited new functional groups (vinyl and hydroxyl) and possible intermolecular recombination, producing an oxidized-polycaprolactone (PCL-OX). Solution viscometry indicated that degradation also occurred during the oxidation reactions (30% drop in viscosity average molecular weight was detected). Differential scanning calorimetry (DSC) also indicated that PCL was chemically modified and degraded. The successive self-nucleation/annealing (SSA) treatment confirmed that a reduction (or interruption) in line...
One-electron oxidation of several derivatives of pyrazolin-5-one, including the drug antipyrine, were studied by pulse radiolysis of aqueous solutions. All the compounds were found to be oxidized by Br2 rapidly but considerably more slowly by weaker oxidants, such as peroxyl radicals. From redox equilibria using p-methoxyphenol and N,N,N',N'-tetramethyl-p-phenylenediamine as reference compounds, the one-electron oxidation potentials of the methyl-substituted 2-pyrazolin-5-ones were found to be in the range of 0.32-0.39 V versus normal hydrogen electrode. The relevance of these findings to the properties of the drug nafazatrom is discussed. Antipyrine was found to have a much higher oxidation potential, estimated as 1.2-1.5 V, which is rationalized on the basis of the phenyl substitution and lack of resonance stabilization of the radical cation.
The chemical composition and the semiconducting properties of passive films formed on nickel based alloy (Alloy 600) in acidic sulphate solution, pH 2.0 at room temperature were studied using Auger analysis, voltammetric techniques and the Mott-Schottky approach. The results obtained revealed that the presence of both chromium and mixed nickel-iron oxides in the films leads to the development of a p-n heterojunction, which controls their electronic structure, similarly manner to the case of stainless steels and Alloy 600 in borate buffer solution. This behavior has been interpreted as representing of an oxide system, which has a duplex character, with an inner p-type semiconducting region, mainly formed by chromium oxide and an outer n-type semiconducting region, containing iron oxide. It could also be observed that the nickel oxide present in the films acts as a barrier layer ...
The chemical composition and the semiconducting properties of passive films formed on nickel based alloy (Alloy 600) in acidic sulphate solution, pH 2.0 at room temperature were studied using Auger analysis, voltammetric techniques and the Mott-Schottky approach. The results obtained revealed that the presence of both chromium and mixed nickel-iron oxides in the films leads to the development of a p-n heterojunction, which controls their electronic structure, similarly manner to the case of stainless steels and Alloy 600 in borate buffer solution. This behavior has been interpreted as representing of an oxide system, which has a duplex character, with an inner p-type semiconducting region, mainly formed by chromium oxide and an outer n-type semiconducting region, containing iron oxide. It could also be observed that the nickel oxide present in the films acts as a barrier layer ...
Conductivity and Hall effect measurements were made in dark and IR-photoexcited p-type ZnTe samples between 77 and 300 K. Acceptor vacancy complexes of activation energies 0.09-0.1 eV were found to be present in the photoexcited samples. Different possible scattering mobilities were considered for both samples to explain the observed hole mobility. In the photoexcited sample a scattering mobility due to vacancy complexes was suggested for the first time to explain the results. The scattering centres were associated with native vacancy complexes segregated at the dislocations sites. The expression for the complex scattering mobility has been deduced using the curve fitting method to be {mu}{sub C}=(6.6x10{sup -11})T{sup 5} e{sup 725/T}. (orig.).
Based on the X-ray crystallographic data of Tc-complexes for brain imaging agents, geometry optimizations in vacuo of TcO-BAT, TcO-MAMA, TcO-L, L-ECD, TcN-BAT and TcN-L, L-ECD complexes are performed with Hartree-Fock method and LANL 2 DZ basis set of G98W program. Then solvation free energy for each Tc-complex mentioned above in water is calculated by polarizable continuum method (PCM) including models of CPCM and IEFPCM. The results show that solvation free energy of Tc-complex is not only an indicator of lipophilicity but also one of the important factors that influence the brain uptake
Complex numbers are an intrinsic part of the mathematical formalism of quantum theory and are perhaps its most characteristic feature. In this article, we show that the complex nature of the quantum formalism can be derived directly from the assumption that a pair of real numbers is associated with each sequence of measurement outcomes, with the probability of this sequence being a real-valued function of this number pair. By making use of elementary symmetry conditions, and without assuming that these real number pairs have any other algebraic structure, we show that these pairs must be manipulated according to the rules of complex arithmetic. We demonstrate that these complex numbers combine according to Feynman's sum and product rules, with the modulus-squared yielding the probability of a sequence of outcomes.
Scandium reacts with 4-(2-pyridylazo)resorcinol in the presence of monocarboxylic acids (X) to form mixed-ligand complexes with a Sc:PAR:x ratio of 1:2:2. The chemical nature of this interaction has been established, and the extraction of these mixed-ligand complexes has also been investigated; stability constants and molar extinction coefficients have been calculated. The values of the latter decrease in the order CH_3COOH > CH_2ClCOOH > CCl_3COOH. The formation and extraction of mixed-ligand complexes in Sc-PAR-HX systems make it possible to increase the sensitivity and selectivity of scandium determination in comparison with the use of the Sc-PAR mono-ligand complex.
Complex I (NADH:ubiquinone oxidoreductase) is the largest enzyme of the mitochondrial respiratory chain. Compared to its bacterial counterpart which encompasses 14-17 subunits, mitochondrial complex I has almost tripled its subunit composition during evolution of eukaryotes, by recruitment of so-called accessory subunits, part of them being specific to distinct evolutionary lineages. The increasing availability of numerous broadly sampled eukaryotic genomes now enables the reconstruction of the evolutionary history of this large protein complex. Here, a combination of profile-based sequence comparisons and basic structural properties analyses at the protein level enabled to pinpoint homology relationships between complex I subunits from fungi, mammals or green plants, previously identified...
Since the elucidation of the structure of double helical DNA, the construction of small molecules that recognize and react at specific DNA sites has been an area of considerable interest. In particular, the study of transition metal complexes that bind DNA with specificity has been a burgeoning field. This growth has been due in large part to the useful properties of metal complexes, which possess a wide array of photophysical properties and allow for the modular assembly of an ensemble of recognition elements. Here we review recent experiments in our laboratory aimed at the design and study of octahedral metal complexes that bind DNA non-covalently and target reactions to specific sites. Emphasis is placed both on the variety of methods employed to confer site-specificity and upon the many applications for these complexes. Particular attention is given to the family of complexes ...
Since the elucidation of the structure of double helical DNA, the construction of small molecules that recognize and react at specific DNA sites has been an area of considerable interest. In particular, the study of transition metal complexes that bind DNA with specificity has been a burgeoning field. This growth has been due in large part to the useful properties of metal complexes, which possess a wide array of photophysical attributes and allow for the modular assembly of an ensemble of recognition elements. Here we review recent experiments in our laboratory aimed at the design and study of octahedral metal complexes that bind DNA non-covalently and target reactions to specific sites. Emphasis is placed both on the variety of methods employed to confer site-specificity and upon the many applications for these complexes. Particular attention is given to the family of complexes ...
An inclusion complex between imazalil (IMZ), a selected fungicide, and cyclomaltoheptaose (beta-cyclodextrin, betaCD) was obtained using supercritical fluid carbon dioxide. The best preparation conditions were determined, and the inclusion complex was investigated by means of 1H NMR spectroscopy in aqueous solution and 13C CPMAS NMR spectroscopy in the solid state. Information on the geometry of the betaCD/IMZ complex was obtained from ROESY spectroscopy, while the dynamics of the inclusion complex in the kilohertz range was obtained from the proton spin-lattice relaxation times in the rotating frame, T(1rho) (1H). PMID:14553984
Two transition metal ions (Cu^2^+ and Co^2^+) and two rare earth metal ions (Ce^3^+ and La^3^+) were used as the assisted metal ions, respectively to prepare the transition metal and rare metal assisted Fe bimetallic amidoximated polyacrylonitrile (AO-PAN) fiber complexes. And their coordination configuration and visible light adsorption properties were examined by coordination number determination and UV-vis-DRS. Then the catalytic performance of these complexes was evaluated as the heterogeneous Fenton catalysts in Rhodamine B degradation by changing the nature and dosage of the assisted ions added. The results indicated that the incorporation of the assisted metal ions led to Fe bimetallic AO-PAN complexes with the more unsaturated configurations than Fe monometallic AO-PAN complex due ...
Absorption spectra of the visible I_2 band of I_2 complexes with Et_2O, Et_2S, and Et_2Se in heptane have been measured up to 3300 bar at 25"0C. The equilibrium constants and volume changes accompanying complex formation, the molar extinction coefficients and the absorption maxima have been estimated. The volume changes were found comparable with those estimated from the X-ray data of the I_2 complexes in the crystalline state. The enhancement of the molar extinction coefficient and the blue shift of the visible I_2 band with increasing pressure have been established. The results suggest a decrease in the bond distance between an n-donor and I_2, compared with the spectroscopic properties of the I_2 complex at 1 bar. The decrease has been estimated as 0.008 nm with increasing pressure up to 3300 bar. (author).
The availability of dimeric Pt(I) complexes with bridging bis(diphenylphosphino)methane ligands, (L--L')/sup n+/, presents an opportunity to study the physical properties and reactivity of metal-metal bonds as a function of the ligand trans to it with a minimum of competing variables. Several interesting trends of Pt-P coupling constants with the Pt-L and Pt-Pt bond lengths in Pt(I) dimers, (L--L')/sup n+/, and structurally related Pt(II) complexes are reported here. The data indicate that the Pt-P coupling constants continue to be sensitive indicators of not only the structure and stereochemistry of platinum phosphine complexes but also the electronic and steric influences of the ligand in such complexes, 23 references, 1 figure, 4 tables.
A-posteriori probability (APP) receivers operating over multiple-input, multiple-output channels provide enhanced performance at the cost of increased complexity. However, employing full APP processing over favorable transmission environments, where less efficient approaches may already provide the required performance at a reduced complexity, results in waste of resources (e.g, processing energy/power). Therefore, for slowly varying channel statistics, substantial complexity savings can be achieved by simple adaptive schemes which perform performance tracking and adjust the complexity of the soft output sphere decoder by adaptively setting the related log-likelihood ratio (LLR) clipping value.
Dust particles in a plasma are charged negatively and are subject to various types of forces, including a drag force by plasma particles and a force due to the collective nature of a plasma. Dust particles are found in a sheath in laboratories balanced by the gravitational force and the electric force, while dust particles in space are ubiquitous, including planetary magnetospheres and interstellar space. Because of the novel nature of a complex system involving plasma particles and dust particles in a collective way, the dusty plasma is often called a complex plasma. The complex plasma is characterized by two distinctly different scales in time and in space. The plasma with electrons, ions and neutrals is characterized by the collective motion with a fast time scale and a short wavelength, while the dust particles move in a slow time scale and a long spatial scale. Some fundamental aspects of a complex ...
A new procedure for preparing an 211At-labeled radiopharmaceutical is suggested. The 211At? anion forms a strong bond with the Rh3+ cation incorporated in the complex with a thiother ligand, 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (16-S4-diol). The reaction conditions are optimized with 131I as astatine analog. The complexes are studied by paper electrophoresis, ion exchange, and thin-layer chromatography. The kinetics of the addition of the 131I? anion to Rh(16-S4-diol) and the dependence of the yield of the forming complex 131I-Rh(16-S4-diol) on the temperature, solution acidity, and reactant concentrations are examined. Taking into account the results obtained, the complex 211At-Rh(16-S4-diol) is prepared by adding astatide (211 At?) to equivalent amounts of RhCl3 and the tetrathioe...
The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern ...
Transient experiments in a Temporal Analysis of Products (TAP) Reactor were performed to elucidate the role of surface oyxgen species in the oxidation of benzene to phenol on ZSM-5 type zeolites with nitrous oxide as a selective oxidant. It was shown by puls experiments with nitrous oxide that the mean lifetime of the generated surface oxygen species is between 0.2s at 500 C and about 4.2 s at 400 C. Afterwards the surface oxygen species desorb as molecular oxygen into the gas phase where total oxidation will take place if hydrocarbons are present. Dual puls experiments consisting of a nitrous oxide puls followed by a benzene puls allowed studying the reactivity of the surface oxygen species formed during the first puls. The observation of the phenol formation was impeded due to the strong sorption of phenol. Multipulse experiments were necessary to reach a ...
A thermal analyzer-differential scanning calorimeter-mass spectrometer (TG-DSC-MS) was used to study oxygen carriers (OC) for their potential use for the application of chemical looping combustion (CLC) to solid fuels. Reaction rates, changes in reaction rates with repeated oxidation-reductions, exothermic heats during oxidation, and the effect of changing reduction gas compositions were studied. Oxidation rates were greater than reduction rates and reaction rates were reproducible through multiple oxidation-reduction cycles except where agglomeration occurred with powders. Iron oxide (Fe{sub 2}O{sub 3} powder) and iron-based catalysts were found suitable for CLC of solid fuels having rapid reduction rates which increased with higher reducing gas concentrations. Fe{sub 2}O{sub 3} powder was used to oxidize a high carbon coal char in an inert gas removing 88% of ...
Slurry aluminizing is one method of protecting titanium alloys and intermetallics at temperatures at which oxidation would otherwise significantly degrade mechanical properties. The technique produces a continuous layer of alumina-forming TiAl_3 on exposed surfaces. The influence of composition, film thickness, and diffusion temperature upon the oxidation resistance of these slurry aluminides was studied in cyclic tests to 816degC (1500deg F). Degradation of slurry aluminized #beta#-titanium alloy and #alpha#-Z titanium aluminide intermetallic occurs by localized oxidation at cracks in the coating layer. These cracks are probably due to mismatch of coefficients of thermal expansion between the coatings and substrates. Addition of silicon to the slurry modifies the oxidation behaviour around a crack by introducing a continuous layer of titanium silicide at the boundary of the aluminide coating and ...
The generation of acidic mine drainage is based on the oxidation dissolution of sulfide minerals due to the contact of ores with the natural water and the air. Namely, the sulfuric acid promotes the dissolution of sulfide minerals and gangue minerals, and Fe{sup 2+} is further oxidized to turn into Fe{sup 3+}, which acts as an oxidizer for other sulfide minerals and promotes the dissolution of the same. This paper roughly describes a mine drainage treatment focusing on an Fe{sup 2+} neutralization method and an iron bacteria oxidation method. The iron bacteria oxidation method is a method of oxidizing Fe{sup 2+} into Fe{sup 3+} by using iron bacteria, and then removing Fe{sup 3+} with calcium carbonate. This method has been used for treating the drainage in the Sakuhara Mine and the former Matsuo Mine, with good results. The paper finally introduces, as ...
Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions - with and without in situ wet oxidation - were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 deg. C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and ...
A duplex surface treatment technique based on calorizing and plasma nitriding was developed to improve the wear and oxidation resistance of H13 steel at high temperatures. The effects of the relative thickness of the calorized layer to the depth of plasma nitriding on the wear and oxidation properties at temperatures up to 900 C were investigated in this work. High-temperature wear tests were performed at 500 C with dry conditions in open air using a ball-on-disk type tribotest machine. Isothermal oxidation tests were performed at 900 C for up to 100 h under controlled atmosphere. The results indicated that the specimens with a calorized layer as an intermediate phase between the surface duplex layer and the base metal showed higher wear and oxidation resistance than the specimens with a nitrided layer alone. During exposure to elevated temperatures, the aluminum in the calorized layer diffused to the ...
Papers are presented on the development of oxidation- and sulfidation-resistant ferritic alloys; the microstructural stability of sulfidation-resistant FeCrAl stainless steels around 500 C; age hardening in Fe-Mn-Al-C austenitic alloys; the oxidation/corrosion behavior of low-Cr Fe-Cr-Ni alloys containing Zr or Nb; the high temperature oxidation/corrosion of iron-based superalloys; and the role of Mo in the Na/sub 2/SO/sub 4/ induced corrosion of superalloys at high temperature. Topics discussed include the effect of variations of Co content on the cyclic oxidation resistance of selected Ni-base superalloys; high temperature oxidation of Fe based alloys; the morphological development of high temperature oxide scales of Fe-Mn-Al base alloys; and the oxidation of an Fe-Mn-Al-C alloy at 1000 C. Consideration is given to the corrosion properties ...
Despite the rapid development of literature pertaining to fundamental (1-4) studies of oxidation catalysis, a general theory of heterogeneous selective oxidation catalysis explaining the selectivity behavior of different metal oxide systems has not yet been developed. Redox mechanisms have been widely invoked in the kinetic and mechanistic descriptions of selective oxidation reactions, suggesting a dynamic behavior of hydrocarbon and oxygen interactions with the catalyst surface. Nevertheless, most of the recent theoretical approaches of this subject matter (5-7) are essentially static in nature. Correlations are made with surface structure on the basis of crystallographic considerations with selectivity being related to the nature, number, bond-strength and nearness of oxygen atoms in the neighborhood of adsorption centers. The effect of the reaction medium on the configuration of the catalyst surface, ...
New tetradentate N(2)O(2) donor Schiff bases and their mononuclear Co(II), Ni(II), Cu(II), and Pd(II) complexes were synthesized and characterized extensively by IR, (1)H-, (13)C-NMR, mass, ESR, conductivity measurements, elemental and thermal analysis. Specifically the magnetic and electronic spectral measurements demonstrate the octahedral structures of cobalt(II), nickel(II) complexes and square planar geometries of copper(II), palladium(II) complexes. All the ligands and complexes were screened for their in vitro antibacterial activity against two gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus) and two gram-negative bacteria (Escherichia coli, Klebsiella pneumonia). In this study, Pd(II) complexes exhibited potent antibacterial activity against B. subtilis, S. aureus whereas other metal complexes also exerted good activity towards all ...
New oxomolybdenum(V) complexes MoOClL (where LH/sub 2/ = Schiff base) derived from ethanolamine and salicylaldehyde, 5-chlorosalicylaldehyde, 5-bromosalicylaldehyde, 5-nitrosalicylaldehyde, 3-ethoxysalicylaldehyde and 2-hydroxy-1-naphthaldehyde have been synthesized and characterised by elemental analyses, conductance, molecular weight, I.R. and electronic spectra and magnetic measurements. The Schiff bases behave as dibasic tridentate ONO donor ligands. The complexes are non-electrolytes and dimers. The complexes exhibit subnormal magnetic moments and are involved in antiferromagnetic exchange with S = 0 ground state. The complexes exhibit electronic spectral bands at ca. 13000 and ca. 17000 cm/sup -1/ due to the transitions dsub(xy)- > dsub(xz,yz) (/sup 2/B/sub 2/- > /sup 2/E) and dsub(xy)- > dsub(x2-y2) (/sup 2/B/sub 2/- > /sup 2/B/sub 1/), respectively. The ..nu..(Mo = O) frequency of ...
New oxomolybdenum(V) complexes MoOClL (where LH_2 = Schiff base) derived from ethanolamine and salicylaldehyde, 5-chlorosalicylaldehyde, 5-bromosalicylaldehyde, 5-nitrosalicylaldehyde, 3-ethoxysalicylaldehyde and 2-hydroxy-1-naphthaldehyde have been synthesized and characterised by elemental analyses, conductance, molecular weight, i.r. and electronic spectra and magnetic measurements. The Schiff bases behave as dibasic tridentate ONO donor ligands. The complexes are non-electrolytes and dimers. The complexes exhibit subnormal magnetic moments and are involved in antiferromagnetic exchange with S = 0 ground state. The complexes exhibit electronic spectral bands at ca. 13000 and ca. 17000 cm"-"1 due to the transitions dsub(xy)->dsub(xz,yz) ("2B_2->"2E) and dsub(xy)->dsub(x2-y2) ("2B_2->"2B_1), respectively. The #nu#(Mo=O) frequency of the complexes is observed in the ...
Absorption spectra of the CT bands of I_2 complexes with Et_2O, Et_2S, and Et_2Se in heptane have been measured up to 4400 bar at 25"0C. The equilibrium constants and the volume changes accompanying complex formation, and the molar extinction coefficients and absorption maxima have been estimated. The volume changes were comparable with those estimated by the visible I_2 bands and by the X-ray data of the I_2 complexes in the crystalline state. In the CT bands of Et_2S-I_2 and Et_2Se-I_2 complexes inversion of shift from red to blue has been observed with increasing pressure though the CT band of Et_2O-I_2 complex shifted only through red. This inversion appears to be characteristic of the strong CT complex. Enhancement of the molar extinction coefficient of the CT band has been found with increasing pressure suggesting enhancement of the CT interaction between ...
No-carrier-added astatine radionuclides produced in the {sup 7}Li-irradiated lead matrix were separated from bulk lead nitrate target by complexing At with insulin, followed by dialysis. The method offers simultaneous separation of At from lead as well as its complexation with insulin. The At-insulin complex might be a potential radiopharmaceutical in the treatment of hepatocellular carcinoma. The stability of At-insulin complex was checked by dialysis against deionized water and Ringer lactate (RL) solution. It has been found that the half-life of At-insulin complex is about {approx}12 h, when dialyzed against deionized water and is only 6 h, when dialyzed against RL solution having the same composition as blood serum. The 6 h half-life of this Insulin-At complex is perfect for killing cancer cells from external cell surfaces as the half-life of internalization ...
No-carrier-added astatine radionuclides produced in the "7Li-irradiated lead matrix were separated from bulk lead nitrate target by complexing At with insulin, followed by dialysis. The method offers simultaneous separation of At from lead as well as its complexation with insulin. The At-insulin complex might be a potential radiopharmaceutical in the treatment of hepatocellular carcinoma. The stability of At-insulin complex was checked by dialysis against deionized water and Ringer lactate (RL) solution. It has been found that the half-life of At-insulin complex is about #approx#12 h, when dialyzed against deionized water and is only 6 h, when dialyzed against RL solution having the same composition as blood serum. The 6 h half-life of this Insulin-At complex is perfect for killing cancer cells from external cell surfaces as the half-life of internalization of ...
From the alkalised crude extract of Symphytum cordatum (L.) W.K. roots, pyrrolizidine alkaloids (PAs) were extracted as free tertiary bases and polar N-oxides in a merely one-step liquid-liquid partitioning (LLP) in separation funnel and subsequently pre-fractionated by preparative multiple-development (MD) thin-layer chromatography (TLC) on silica gel plates. In this way three alkaloid fractions of different polarities and retention on silica gel plates were obtained as: the most polar N-oxides of the highest retention, the tertiary bases of medium retention, and diesterified N-oxides of the lowest retention. The former fraction was reduced into free bases by sodium hydrosulfite and purified by LLP on Extrelut-NT3 cartridge. It was further analysed together with the two other fractions by high-performance liquid chromatography (HPLC)-ion-trap mass spectrometry with atmospheric pressure chemical ionization (APCI) interface ...
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO{sub 2}, PrO{sub 2}), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two shapes: small cubic (oxide) and large plate-like (tetragonal) structures. The ...
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO2, PrO2), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two shapes: small cubic (oxide) and large plate-like (tetragonal) structures. The conversion ...
Basic studies of the oxidation resistance of Fe-Cr binary and Fe-Cr-Ni ternary alloys in pure oxygen have shown that the excellent corrosion resistance of Alloy 800 is explicable in terms of the low defect concentrations and diffusion rates in the oxide forming on alloys of this composition in sufficiently oxidising environments. The performance of Alloy 800 in environments of particular importance to nuclear power generation is briefly reviewed to determine to what extent ideas derived from the basic studies of Fe-Cr-Ni ternary alloys are borne out in practice. The good corrosion resistance of Alloy 800 in steam and CO_2 and, to some extent, in molten salt environments is in agreement with the behaviour of ternary alloys in oxygen. Minor aliovalent alloying additions are only expected to have a significant effect on the oxidation resistance of Alloy 800 if they favour the formation of breakthrough duplex ...
The aim of this work is to test the catalytic oxidation of pyridine over zeolite-supported catalysts and to compare the difference in their activities for the oxidation of pyridine. The catalytic oxidation of pyridine pollutant on a series of copper-supported catalysts, inclusive of Cu/beta, Cu/ZSM-5, Cu/MCM-41 and Cu/{gamma}-Al{sub 2}O{sub 3}, in the presence of excess oxygen was studied. The activity of the copper-supported catalysts for the pyridine oxidation could be correlated with the binding energy of oxygen coordinated to metal copper, while the ability to control the yield of NO{sub x} appeared to be strongly dependent on the binding energy of NO bonded to metal copper. On these catalysts, two copper species, Cu(H{sub 2}O){sub 6}{sup 2+} ions and CuO were identified, in which Cu{sup 2+} ions had higher activity for the NO{sub x} control but poorer activity for the pyridine ...
Dominating factors in plasma nitriding and plasma condition that makes nitriding possible in plasma nitriding process of metals having hard oxide film were studied. In case of stainless steel, oxide film sputtering was easier comparing to nitriding layer. Three phenomena such as sputtering of oxide layer, formation of nitriding layer and sputtering of nitriding layer occurred simultaneously. Nitriding was achieved when the formation of nitriding layer reached the peak comparing to the removal of nitriding layer after the removal of oxide layer. Situations of metallic surface of stainless steel in surface nitriding were divided into four categories and they were, situation where oxide layer remained as it is, situation where nitriding layer was formed although oxide layer remained in some part, situation where only nitriding layer was formed and situation where ...
Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on ...
A laboratory-scale well-mixed thermostatic reactor with continuously blasting air was used to investigate the oxidation inhibition of sulfite in dual alkali flue gas desulfurization (FGD) system. The effects of operating parameters such as pH value and catalyst concentration on the oxidation were studied. Sodium thiosulfate was used in the system, and was found that it significantly inhabited the sulfite oxidation. In the absence of catalyst, sodium thiosulfate at 12.67 mmol/L had an inhibition efficiency of approximately 98%. While in the presence of catalyst, sodium thiosulfate at 26.72 mmol/L had an inhibition efficiency less than 85.0%. The oxidation reaction order of sulfite in the sodium thiosulfate was determined to be -1.90 and -0.55 in the absence and presence of the catalyst, respectively. Apparent activation energy of oxidation inhibition was calculated to be 53.9 kJ/mol. ...
Boron is implanted in crystalline silicon through oxide layers with different thicknesses. The implantation is carried out at various doses and energies of interest in ultra large scale integration (ULSI) application. Rapid thermal annealings (RTA) are used to obtain shallow junctions and electrical activation of the B atoms. However, transient enhanced diffusion induced by implantation damage can be observed. The boron concentration profiles before and after annealing are obtained with secondary ion mass spectrometry (SIMS). It is found that the diffusion transient in the tail region of the boron profile increases with decreasing oxide thickness. Even more, if the implantation damage concerns mostly the oxide, i.e. when the concentration peak is located in this oxide, the oxygen knocked into the silicon substrate could play this way an important role in restricting the boron diffusion, which is good to ...
Boron is implanted in crystalline silicon through oxide layers with different thicknesses. The implantation is carried out at various doses and energies of interest in ultra large scale integration (ULSI) application. Rapid thermal annealings (RTA) are used to obtain shallow junctions and electrical activation of the B atoms. However, transient enhanced diffusion induced by implantation damage can be observed. The boron concentration profiles before and after annealing are obtained with secondary ion mass spectrometry (SIMS). It is found that the diffusion transient in the tail region of the boron profile increases with decreasing oxide thickness. Even more, if the implantation damage concerns mostly the oxide, i.e. when the concentration peak is located in this oxide, the oxygen knocked into the silicon substrate could play this way an important role in restricting the boron diffusion, which is good to ...
In this work we present an ultra-low temperature method for the oxidation of an amorphous silicon-carbide-nitride (SiCN) material. The SiCN is deposited on silicon substrates by plasma enhanced chemical vapor deposition using CH{sub 4}, SiH{sub 4}, and N{sub 2} chemistry. The physical and chemical properties are characterized for the as-deposited SiCN and post-oxidized films are discussed. The SiCN film is exposed to oxygen plasma, where it undergoes a chemical transformation into a binary SiO{sub 2} material system. A 1.7 nm/min oxidation rate is typical for this process and compares favorably to oxidation methods utilizing much higher temperatures. The substrate temperature remains extremely low throughout the oxidation process, T{sub s} < 200 deg. C. Changes in film stress, optical constants, film thickness, surface roughness, and film density are measured. Chemical ...
Technetium-99m was previously shown to form a stable, neutral and lipopholic complex with propylene amine oxime, PnAO. This Tc-99m-PnAO complex was shown to efficiently extracted by normal brain. However, it is not sufficiently retained in the brain to image its cerebral distribution using convertional SPECT (single-photon emission computerized tomography) instrumentation. A number of derivatives of PnAO have been synthesized and their technetium-99m complexes have been biologically evaluated. A number of these have been shown to have high brain uptake without exhibiting the rapid cerebral clearance that was observed with Tc-99m-PnAO. To better understand the chemistry of these potential brain imaging agents, a number of technetium-99 complexes of derivatives of PnAO have been synthesized and characterized. Substituents on the tetradentate amine oxime backbone were varied to probe the effect(s) of these ...
The method of proton magnetic resonance (PMR) has been used to study the mechanism of reaction of complexing of paramagnetic Pr/sup 3 +/ ion with ethylenediaminetetra acetic acid (EDTA). The influence of medium acidity (pH5-12), EDTA/Pr ratio varying from 1 to 50, Pr/sup 3 +/ ion concentration (from 5x10/sup -3/ to 3x10/sup -1/ g-ion/l) and temperature (8-98 deg C) on chemical shifts and broadening of signals of EDTA molecule protons is investigated. Data on ratio of components, coordination and stability of forming complexes are obtained. The existence of two types of complexes with the Pr/EDTA ratio equal to 1:1 and 1:2 has been found. Equimolecular complex (1:1) is stable all over the studied temperature interval in contrast to the complex 1:2 for which at 50 deg C fast extrasphere exchange (Pr EDTA)EDTA * + EDTA/sup 0/ reversible (PrEDTA)EDTA/sup 0/ + EDTA * is observed, while ...
Several dioxomolybdenum(VI) complexes of the schiff bases derived from salicylaldehyde, 2-hydroxy-1-naphthaldehyde, o-hydroxyacetophenone or pyridoxal and o-aminobenzylalcohol, o-aminophenol, o-hydroxybenzylamine, o-hydroxy(methylbenzyl)amine or 3-amino-2-naphthoic acid have been synthesized and characterized by elemental analysis, electrical conductance, molecular weight, IR and electronic spectral and magnetic susceptibility measurements. The schiff bases behave as dibasic, tridentate ligands and coordinate through ONO donor system forming complexes of the type MoO_2L.X (where LH_2=schiff base, X=H_2O or Ch_3OH). The compounds MoO_2L.Ch_3OH react with 2,2'-dipyridyl to form heterochelates of the type MoO_2L.dipyridyl. The complexes are non-electrolytes, monomers, diamagnetic and possess a cis-MoO_2 structure. The complexes exhibit a ligand-to-metal charge-transfer transition around 25000 cm"-"1. The ...
Antitumor platinum(II) complexes derived from N-alkyl-propanediamine differing in the length of their carbon chain (C8, C10, C12 and C14) were incorporated in liposomes and the cytotoxic activity of these formulations was evaluated against tumor (A{sub 549}, MDA-MB-231, B16-F1 and B16-F10) and non-tumor (BHK-21 and CHO) cell lines. Stable and monodisperse liposome suspensions incorporating the platinum complexes were obtained from the lipid composition consisting of distearoyl-sn-glycero-3-phosphocholine, cholesterol and 1,2-distearoyl-sn-glycero- 3-phosphoethanolamine-N-(methoxy(polyethylene glycol)-2000) at 5:3:0.3 molar ratio. The entrapment efficiency (EE%) of the platinum complexes in liposomes increased with the carbon chain length. EE% was higher than 80% in C12- and C14-derivatives. The effect of liposome encapsulation on the cytotoxic activity of the complexes was found to depend on the carbon ...
Extraction of copper-, nickel-, zinc- and cadmium complexes with 4-(2 pyridilazo)-resorcin (PAR) is studied in the presence of 2-aminopyridine (Am). Maximum optical densities of the extracts are attained at pH=7.5-8.0; 6.0-7.0; 6.5-7.0 and 7.0-8.0, respectively. The ratio of components in the complexes extractable by chloroform was defined by the method of isomolar series and equilibrium shift. It is established that nickel and copper are extracted to the organic phase as the NiAm(PAR)_2 and CuAmPAR complexes, and, in the case of zinc and cadmium, complexes of different composition are extracted, for example Zn(Am)_2PAR and ZnAm(PAR)_2. The light absorption spectra are studied and molar extinction coefficients of complex extracts are determined at lambdasub(max). It is shown that the general low of light absorption is observed within a sufficiently wide range of concentrations for ...
Let $M$ be a complex manifold of complex dimension $n+k$. We say that the functions $u_1,...s,u_k$ and the vector fields $\\xi_1,...,\\xi_k$ on $M$ form a \\emph{complex gradient system} if $\\xi_1,...,\\xi_k,J\\xi_1,...,J\\xi_k$ are linearly independent at each point $p\\in M$ and generate an integrable distribution of $TM$ of dimension $2k$ and $du_\\alpha(\\xi_\\beta)=0$, $\\d^c\\u_\\alpha(\\xi_\\beta)=\\delta_{\\alpha\\beta}$ for $\\alpha,\\beta=1,...,k$. We prove a Cauchy theorem for such complex gradient systems with initial data along a $\\CR-$submanifold of type $(\\CRdim,\\CRcodim)$. We also give a complete local characterization for the complex gradient systems which are \\emph{holomorphic} and \\emph{abelian}, which means that the vector fields $\\xi_\\alpha^c=\\xi_\\alpha-J\\xi_\\beta$, $\\alpha=1,...,k$ are holomorphic and satisfy $[\\xi_alpha^c,\\bar{\\xi_\\beta^c}]=0$ ...
Chelating tendencies of several biologically important compounds viz. glycocyamine (GCN: N-amidino-aminoethanoic acid) taurine (TRN: 2-aminoethanesulphonic acid) and pyridoxal [PDL: 3-hydroxy-5-(hydroxymethyl)-2-methyl-pyridine-4-carbaldehyde] have been examined by pH-metric titration technique in their binary complex formation with copper(II) and uranyl(VI) ions. The work has further been extended to investigating the ternary complex formation involving 2.2'-bipyridine. 1,10-phenanthroline or nitrilotriacetic acid as a primary and TRN and PDL as secondary ligands. All the experiments were carried out at 25"0C and at an ionic strength of 0.1M (NaCl0_4) in aqueous or 50% (v/v) aqueous-ethanol medium according to the suitability of the experimental conditions. Stabilities of ternary complexes as compared to those of the corresponding binary complexes of the secondary ligands have also been discussed. ...
'The interactions of carbon tetrachloride with strongly basic oxides and hydroxides have been studied by several techniques in order to understand the surface reactions and the subsequent bulk reactions that result in the destruction of the chlorinated hydrocarbon. Emphasis has been placed on understanding the surface phases, as well as the bulk phases, that are present during these transformations. As a result of the study with barium oxide, a reaction cycle has been demonstrated that may have practical significance in the removal of chlorinated hydrocarbons.'
In most industrial processes operating at elevated temperatures, protective oxide layers perform a vital duty in protecting the underlying metallic alloys from process gases. Coal-fired combined cycle power generation systems present a number of process conditions in which the properties of the protective oxide layers are particularly important. This paper discusses two of these particular conditions: (1) `erosion/corrosion` of in-bed heat exchanger tubing and (2) thermal cycling of hot gas path components. For both these situations, the desirable properties of protective scales are outlined. The behaviour of scales in practice are highlighted. 33 refs., 6 figs., 2 tabs.
Chlorophyll a, chlorophyll b, and bacteriochlorophyll a in aqueous micellar solutions of Trition X 100 (2%) are readily oxidized by pulse-radiolytically generated N_3., Br_2"-., and (SCN)_2"-. radicals at nearly diffusion-controlled rates. The kinetic study suggests that pigment molecules occupy multiple sites in the micelle. Pheophytin a is only oxidized by N_3. and Br_2"-. radicals. The absolute spectra and the molar extinction coefficients of chlorophyll a, bacteriochlorophyll a, chlorophyll b, and pheophytin a cations have been determined. The chlorophyll a cation has been observed in the presence of pigment aggregates.
Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)
A nitrogen oxides decreasing combustion method comprising: mixing a fuel and air with each other; bringing the mixture obtained into contact with a packed catalyst; and adding a fresh supply of the fuel to the stream obtained to form a mixed gas and causing the mixed gas to undergo non-catalytic thermal combustion, characterized in that only a catalytic reaction or combustion occurs at the packed catalyst; the temperature of the packed catalyst is kept lower than the ignition temperature of the mixture; the adiabatic flame temperature which is reached by the non-catalytic thermal combustion of the mixed gas is lower than the temperature at which the nitrogen oxides occur. 39 figs.
This patent describes a nitrogen oxides decreasing combustion method which comprises: a first step of mixing a fuel and air with each other; a second step of bringing the mixture obtained in the first step into contact with a packed catalyst such that only catalytic combustion occurs; and a third step of adding a fresh supply of the fuel to a stream obtained from the second step to form a mixed gas and causing the mixed gas to undergo non-catalytic thermal combustion. The temperature of the packed catalyst is lower than the ignition temperature of the mixture and the adiabatic flame temperature of the mixed gas is lower than a temperature at which the nitrogen oxides occur.
Several possibilities of the use of molecular models in quantum-chemical investigations of the structure of defect centers on the surfaces of oxides on nontransition elements have been illustrated. There has been a special discussion of the assumption of the local nature of the chemical interactions in these systems, which underlies such an approach, and of the consequent laws governing the formation of their lattices in the example cases of zeolites, kaolinites, and comparable boron- and aluminum-containing oxides. A quantum-chemical interpretation of the body of experimental data from investigations of the dehydroxylation of H forms of zeolites has been given. The structure of the Lewis acid centers formed as a result, and their chemisorption properties, have been discussed.
Cr_2O_3 scales are found to form on Alloy 800 and a similar pure ternary alloy in air, and 1 and 50 atm. helium containing oxidizing impurities typical of those in an SGHTR. The strong temperature dependence and neglibible helium overpressure dependence indicate that gas transport through the scales is not rate controlling. Surface oxidation rates are therefore controlled by solid state diffusion and the low oxygen partial pressure dependence of the oxidation rate in Alloy 800 is ascribed to the presence of extrinsic defects in the Cr_3O_3 (due to doping by alloying elements) or to the presence of short circuit diffusion paths. (Auth.).
We report on the single-particle properties of lanthanide-ion doped oxide nanoparticles. We have demonstrated that their size can be accurately determined from their luminosity. The optically determined size distribution is in very good agreement with the distribution obtained from transmission electron microscopy (TEM). We also showed that the photobleaching of these nanoparticles is related to a reduction process and that we can use it to sense in a concentration-dependent manner the presence of an oxidant like H2O2. Finally, we propose a way to perform nanoparticle-protein coupling and to determine the protein-nanoparticle ratio at the single-particle level.
This work deals with kinetic description of carbothermic reduction of iron oxides using microwaves as power source. Previous researches show that it is possible to conduct this kind of process successfully, but real kinetic comparisons between conventional and microwaves procedure have been presented partially. The aim of this work is to describe reduction kinetics, taking into account how the iron oxide is reduced by microwaves compared with conventional energy supply. In this study the authors used iron ore in pellet shape and dust. They found that both, pellet and dust reduction stops when it reaches approximately 40%, even at whole power.
Lanthanide-ion doped oxide nanoparticles were functionalized for use as fluorescent biological labels. These nanoparticles are synthesized directly in water which facilitates their functionalization, and are very photostable without emission intermittency. Nanoparticles functionalized with guanidinium groups act as artificial toxins and specifically target sodium channels. They are individually detectable in cardiac myocytes, revealing a heterogeneous distribution of sodium channels. Functionalized oxide nanoparticles appear as a novel tool particularly well adapted to long-term single-molecule tracking.
Separation of lithium isotopes was investigated by chemical ion exchange with a hydrous manganese(IV) oxide ion exchanger using an elution chromatography. The capacity of manganese(IV) oxide ion exchanger was 0.5 meq/g. The heavier lithium isotope was enriched in the solution phase, while the lighter isotope was enriched in the ion exchanger phase. The separation factor was determined according to the method of Glueckauf from the elution curve and isotopic assays. The separation factor of {sup 6}Li{sup +} -{sup 7}Li{sup +} isotope pair fractionation was 1.018.
Uranium has varying degrees of oxidation (+4 and +6) and is responsive to changes in the redox potential of the environment. It is deposited at the reduction barrier with the participation of biota and at the sorption barrier under oxidative conditions. Iron (hydr)oxides are the strongest sorbents of uranium. Uranium, being an element of medium biological absorption, can accumulate (relative to thorium) in the humus horizons of some soils. The high content of uranium in uncontaminated soils is most frequently inherited from the parent rocks in the regions of positive U anomalies: in the soils developed on oil shales and in the marginal zone of bogs at the reduction barrier. The development of nuclear and coal-fired power engineering resulted in the environmental contamination with uranium....
One of the main problems related to optical thin film materials used in high power laser environments is the catastrophic damage caused to them due to laser irradiation. While the influence of ion bombardment on the optical properties of oxide thin films is now a well understood subject, the morphology and crystalline behaviour of these films under ion incidence is not so well studied. Hence, it is of great importance to investigate the effects of ion bombardment during growth on the microstructure and crystalline behaviour of oxide materials.
We studied a novel universal spectrochemical series of six-coordinated octahedral 3d transition metal complexes, which can be used for any combination of central metal atom and ligand molecules. A two dimensional spectrochemical series could be used to estimate the ligand field splitting energy of not only known compounds but also the unknown compounds. Therefore, it should be possible to control the physical properties, such as the electronic and magnetic properties and the optical phenomena of octahedral transition metal complexes by modifying the ligand field splitting. PMID:19378561
Advanced techniques for focused-ion-beam (FIB) device modification have been developed for complex, multistep modifications to circuitry on planar chip technology. Applying gas-assisted etching (GAE) techniques for high-aspect-ratio milling and the selective milling of both conductive and insulating films enhances process latitude. Localized ion-beam-induced deposition of an insulating film provides reconstructive capability in previously modified areas. The application of both techniques for complex device modification on VSLI devices fabricated with CMOS process technology is reviewed. (UK).
A few metal complexes of isatin-isonicotinoylhydrazone with Ni(II), Cr(III), Co(II), Cu(II), Zn(II) and Cd(II) have been prepared and characterized on the basis of elemental analyses, infrared and electronic spectra as well as "1H NMR spectra, conductivity and magnetic measurements. In view of the results obtained, it has been found that two molecules of isatin-isonicotinoylhydrazone are chelated to the central metal ion as bis-uninegative ONO tridentate ligand forming non-electrolytic octahedral metal complexes. (author)
Of the radionuclides with physical properties most suited for use with monoclonal antibody for tumor imaging or therapy, few are more available or desirable than Pb-203, 212 and Bi-212. Yet no clinical studies have as yet been possible solely due to the lability in vivo of known complexes. We now report that bismuth complexes of the ligands p-SCN-Bz-DOTA and p-SCN-Bz-trans-cyclohexylDTPA are effective at protecting Bi-206 from release when linked to immunoproteins. Practicable, efficient ligand syntheses will be reported. Initial studies reveal that antibody is labeled efficiently with radiolead DOTA complexes. Preliminary studies indicate stability in vivo.
The Conawapa-Winnipeg Power Transmission Complex includes five interrelated transmission and conversion facilities. This booklet describes work done on the upgrade of the southern receiver system, one component of the complex. The southern receiver system is composed of a network of high voltage transmission lines and station facilities. The booklet includes a description of the upgrade, the project setting, short and long-term effects and impact management, and the next steps to be taken in the process, including the regulatory process and public consultation.
In order to increase the sensitivity of photometric determination of tungsten and to find forms with high molar extinction coefficients, mixed-ligand complexes of tungsten with antipyrine and trihydroxyfluorone have been studied. The molar extinction coefficients have been determined for chloride associates of mixed-ligand complexes containing different trioxyfluorones: phenylfluorone, salicylflourone, p-bromphenylfluorone, anthrafluorone, dioxyfluorescein, and dioxyfluoroscein ethylate (DOFE). An associate formed by DOFE has the maximum molar extinction coefficient. It has been used for photometric determination of microgram amounts of tungsten impurity in vanadyl sulphate.
Central nervous system (CNS) development, homeostasis, stress responses, and plasticity are all mediated by epigenetic mechanisms that modulate gene expression and promote selective deployment of functional gene networks in response to complex profiles of interoceptive and environmental signals. Thus, not surprisingly, disruptions of these epigenetic processes are implicated in the pathogenesis of a spectrum of neurological and psychiatric diseases. Epigenetic mechanisms involve chromatin remodeling by relatively generic complexes that catalyze DNA methylation and various types of histone modifications. There is increasing evidence that these complexes are directed to their sites of action by long non-protein-coding RNAs (lncRNAs), of which there are tens if not hundreds of thousands speci...
Several new complexes of isomeric schiff bases derived from salicylaldehyde and o-hydroxybenzylamine/o-aminobenzyl-alcohol with Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), and Dy(III) have been synthesized and characterized by elemental analysis, molar conductance, IR, electronic spectra and magnetic susceptibility measurements. The schiff bases behave as monobasic tridentate ONO donor and dibasic tridentate ONO donor ligands and form complexes of the type Ln(LH)L. (author). 12 refs.
This Addendum to the Facility Safety Plan (FSP) 360 Complex describes the safety requirements for the safe conduct of all biohazardous research operations in all buildings within the 360 complex program areas. These requirements include all the responsibilities and authorities of building personnel, operational hazards, and environmental concerns and their controls. In addition, this Addendum prescribes facility-specific training requirements and emergency controls, as well as maintenance and quality assurance requirements for ES&H-related building systems.
The mechanistic aspects of electrochemical reductions of U"V"IO_2(acac)_2dmso(acac=acetylacetonate, dmso=dimethyl sulfoxide) complex with bidentate ligand(acac) in DMSO were investigated by using cyclic voltammetry, normal pulse voltammetry, and spectrophotometer equipped with an optical transparent thin layer electrode cell. It is concluded that the uranyl complexes with bidentate ligands at the equatorial plane form stable U(V) complexes by the electrochemical reduction and that their molar extinction coefficients in the visible region are very small. (J.P.N.).
This paper is concerned with the determination of a unique scaling parameter in complex scaling analysis and with accurate calculation of dynamics resonances. In the preceding paper we have presented a theoretical analysis and provided a formalism for dynamical resonance calculations. In this paper we present accurate numerical results for two non-trivial dynamical processes, namely, models of diatomic molecular predissociation and of barrier potential scattering for resonances. The results presented in this paper confirm our theoretical analysis, remove a theoretical ambiguity on determination of the complex scaling parameter, and provide an improved understanding for dynamical resonance calculations in rigged Hilbert space.
This paper studies the sorption of chlorine complexes of ruthenium (IV) on the graft copolymer of a polyacrylonitrile fiber with poly-2-methyl-5-vinylpyridine (PAN-MVP). The composition of the fiber is illustrated. It is shown that sorption of chlorine complexes of ruthenium (IV) from acid solutions by a pyridine fiber sorbent takes place according to an anion-exchange mechanism and is due to the formation of compounds of the diamine type (Ru(RPy)/sub 2/Cl/sub 4/).
A complex network approach on a rough fracture is developed. In this manner, some hidden metric spaces (similarity measurements) between apertures profiles are set up and a general evolutionary network in two directions (in parallel and perpendicular to the shear direction) is constructed. Also, an algorithm (COmplex Networks on Apertures: CONA) is proposed in which evolving of a network is accomplished using preferential detachments and attachments of edges (based on a competition and game manner) while the number of nodes is fixed. Also, evolving of clustering coefficients and number of edges display similar patterns as well as are appeared in shear stress, hydraulic conductivity and dilation changes, which can be engaged to estimate shear strength distribution of asperities.
The US Department of Energy is conducting cleanup operations at the Weldon Spring site, St. Charles, Missouri, that will include development of a 77-ha (191-acre) soil borrow area. Eight wetlands, including riverine and palustrine emergent wetland types and totaling 0.9 ha (2.2 acres), will be eliminated during excavation of the borrow area. A 23-ha (57-acre) wetland/shorebird complex will be created at the Busch Conservation Area. The complex will include 2 ha (5 acres) of palustrine emergent wetland as mitigation for wetland losses in the borrow area.
The oxidation of n-butylbenzene was studied in a jet-stirred reactor (JSR) at 10atm in dilute conditions providing new experimental results over the low- and high-temperature range 550-1180K, and variable equivalence ratio (0.25ϕ1.5). They consisted of concentration profiles of the reactants, stable intermediates and final products, measured as a function of temperature, at a constant residence time of 1s, by sonic probe sampling followed by on-line GC-MS and off-line GC-TCD-FID and GC-MS analyses. The oxidation of n-butylbenzene in these conditions was modeled using a detailed chemical kinetic reaction mechanism (404 species and 2210 reactions, most of them reversible) deriving from a previous scheme proposed for the ignition, oxidation, and combustion of simple aromatics (benzene,...
Senescence is regarded as a physiological response of cells to stress, including telomere dysfunction, aberrant oncogenic activation, DNA damage, and oxidative stress. This stress response has an antagonistically...Full Text Available
familiarity fire triangle (i.e., fuel, oxidant, and ignition source) are excluded. It Is obvious that for the baseline safety goal for spacecraft this ...