A Pd(0)-catalyzed intramolecular Heck-type reaction of oxime ether has been developed, providing convenient access to heterocyclic oximes. PMID:21964259
The mechanism of chemical poisoning of model heterogeneously catalyzedreactions on transition metal surfaces is studied. Clean Mo(001) surfaces were characterized; results suggest a first-layer contraction of 10% of the bulk interlayer spacing. Characterization of clean Co(0001) surfaces is underway. Decomposition of formic acid on Mo(001) surfaces is being studied. (DLC)
This paper reports the effectiveness of solvents on the liquefaction of 11 different Turkish lignites investigated by using tetralin, creosote, and anthracene oils. The highest total conversions were obtained with tetralin. The catalytic effects of CoMo and red mud were compared by using creosote oil as the solvent. It was found that red mud catalyzed mainly the asphaltene formation reaction for the given experimental conditions. The additional of CoMo significantly catalyzed the liquefaction reaction, thus increasing the lignite conversion and oil formation.
The esterification reaction of a long-chain fatty acid and a fatty alcohol catalyzed by sugar ester-modified lipases in organic media was studied. The reaction activity was improved when the lipases were modified with sugar esters. Among four kinds of sugar esters and six kinds of lipases, lipase CES modified with sugar ester SE-7 showed the highest reaction activity. The pH, solvent and temperature on the reaction activity of SE-7 modified lipase CES were also studied. PMID:12142919
To understand more fully the mechanism of enzyme-catalyzed phospho group transfer, the stereochemical course at phosphorus of four enzymes has been determined. First, using adenosine (..gamma..-(S)-/sup 16/O, /sup 17/O, /sup 18/O)triphosphate as the substrate, the reactioncatalyzed by creatine kinase has been found to proceed with overall inversion of configuration at phosphorus. Second, using adenosine (..beta..-(S)-/sup 16/O, /sup 17/O, /sup 18/O)diphosphate as the substrate, the reactioncatalyzed by adenylate kinase has been found also to proceed with overall inversion. Third, the reactioncatalyzed by phosphoenolpyruvate carboxylase has been studied using ((S/sub p/)-/sup 16/O, /sup 17/O)thiophospoenolpyruvate as the substrate in H/sub 2/ /sup 18/O. Fourth, using adenosine 5'-O-((..gamma..S/sub p/)-..beta gamma..-/sup ...
Phenylpropenes, a large group of plant volatile compounds that serve in multiple roles in defense and pollinator attraction, contain a propenyl side chain. Eugenol synthase (EGS) catalyzes the reductive...Full Text Available
The expression of desacetoxyvindoline 4-hydroxylase (D4H), which catalyzes the second to the last reaction in vindoline biosynthesis in Catharanthus roseus, appears to be under complex,...Full Text Available
Unsymmetric diaryl alkynes were synthesized from the palladium-catalyzed decarboxylative coupling of aryl halides and propiolic acid using a continuous flow reaction system. This flow chemistry system continuously gave the desired products in moderate to good yields, and produced less byproduct than was formed in the batch reaction.
Details of a series of reactions for the production of ethylene glycol using a catalyst of Nafion solid perfluorosulfonic acid resin was detailed. The reactions included the carbonylation of formaldehyde and esterification and then hydrogenation of the product of the carbonylation, glycolic acid. Other preparations included in the work included methyl glycolate, acetylglycolic acid, methyl acetylglycolate, and methyl methoxyacetate.
In the course of observing by means of Auger spectroscopy graphite gasification reactionscatalyzed by metals, it has been found that in the presence of hydrogen, nickel appears to diffuse from the surface into the bulk of the graphite. When potassium is deposited on graphite, it is volatilized above 400/sup 0/C. Surprisingly the production of methane and carbon dioxide from the reaction of graphite and steam was catalyzed by potassium at as low a temperature as 250/sup 0/C. It has been shown that literature on the alkylation of benzene with synthesis gas is erroneous and that the products reported are due to Lewis acid catalyzed cracking of benzene. A novel cobalt mediated, reversible cleavage of a vinyl-hydrogen bond has been discovered. All products from the thermal decomposition of tetralin have been identified. The stereochemistry of cis-1, 2 dihydrotetralin was determined. In ...
In this study, a two-step process was developed to produce biodiesel from Calophyllum inophyllum oil. Pre-treatment with phosphoric acid modified b-zeolite in acid catalyzed esterification process preceded by transesterification which was done using conventional alkali catalyst potassium hydroxide (KOH). The objective of this study is to investigate the relationship between the reaction temperatures, reaction time and methanol to oil molar ratio in the pre-treatment step. Central Composite Design (CCD) and Response Surface Methodology (RSM) were utilized to determine the best operating condition for the pre-treatment step. Biodiesel produced by this process was tested for its fuel properties.
Green crab (Scylla serrata) alkaline phosphatase (EC 3.1.3.1) is a metalloenzyme, which catalyzes the nonspecific hydrolysis of phosphate monoesters. The kinetics of inhibition of the enzyme by sodium (2, 2'-bipyridine) oxodiperoxovanadate, pV(bipy), has been studied. The time course of the hydrolysis of p-nitrophenyl-phosphate catalyzed by the enzyme in the presence of different pV(bipy) concentrations showed that at each pV(bipy) concentration, the rate decreased with increasing time until a straight line was approached, the straight line slopes are the same for all concentrations. The results suggest that the inhibition of the enzyme by pV(bipy) is a slow, reversible reaction with fractional remaining activity. The microscopic rate constants are determined for the reaction of inhibitor with the enzyme. PMID:10691182
Enzymatic reactions in non-aqueous media have been shown to be effective in carrying out chemical transformation where the reactants are insoluble in water or water is a byproduct limiting conversion. Ionic liquids, liquid organic salts with infinitesimal vapor pressure, are potentially useful alternatives to organic solvents. It is known that the thermodynamic water activity is an important variable affecting the activity of enzymes in non-aqueous solvents. This study investigated the influence of water activity on the esterification of geraniol with acetic acid in ionic liquid [bmim]PF6 catalyzed by immobilized Candida antarctica lipase B. The conversion of geraniol in [bmim]PF6 was significant although the reaction rate was slower than in organic solvents. The profile of initial reaction rate-water activity was determined experimentally, and differed from the data reported for other non-aqueous ...
N,N-Dialkyl-P-phenylphosphonamidous iodides are formed in the reactions of phenylphosphonus diiodide with silylated secondary amines. N,N-Dialkyl-P-phenylphosphonamidous iodides react with electrophilic reagents (methyl iodide, benzenesulfonyl azide, and phenyl azide) by the usual schemes with the formation of alkylation and oxidative-imination products. Iodine catalyzes the disproportionation of morpholinophenylphosphinous iodide into dimorphomorpholinophenylphosphinous iodide with iodine are iododimorpholinophenylphosphonium triiodide and phenylphosphonous diiodide.
Administration of minocycline (MN), a tetracycline antibiotic, produces a black pigment in the thyroids of humans and several species of experimental animals and antithyroid effects in rodents. We have previously shown that these effects appear to be related to interactions of MN with thyroid peroxidase (TPO), the key enzyme in thyroid hormone synthesis. In the present study, the mechanisms for inhibition of TPO-catalyzed iodination and coupling reactions by MN were investigated. 37 refs., 7 figs., 3 tabs.
The first enzyme-catalyzedreaction leading from indole-3-acetic acid (IAA) to the myo-inositol esters of IAA is the synthesis of indole-3-acetyl-1-O-β-d-glucose...Full Text Available
A method for the hydroconversion of coal by solvent treatment at elevated temperatures and pressure wherein an alcohol having an alpha -hydrogen atom, particularly a secondary alcohol such as isopropanol, is utilized as a hydrogen donor solvent. In a particular embodiment, a base capable of providing a catalytically effective amount of the corresponding alcoholate anion under the solvent treatment conditions is added to catalyze the alcohol-coal reaction.
The authors studied the resolution of racemic glycidol through esterification with butyric acid catalyzed by porcine pancreatic lipase in organic media. A screening of seven solvents (log P values between 0.49 and 3.0, P being the n-octanol-water partition coefficient of the solvent) showed that neither log P nor the logarithm of the molar solubility of water in the solvent provides good correlations between enantioselectivity and the properties of the organic media. Chloroform was one of the best solvents as regards the enantiometic purity (e.p.) of the ester produced. In this solvent, the optimum temperature for the reaction was determined to be 35C. The enzyme exhibited maximum activity at a water content of 13 [plus minus] 2% (w/w). The enantiomeric purity obtained was 83 [plus minus] 2% of (S)-glycidol butyrate and did not depend on the alcohol concentration or the enzyme water content for values of these parameters up to 200 mM and 25% ...
Four high-sulphur low-rank coals have been treated at hydrogenation conditions with three iron-based catalyst precursors: Red Mud (Fe[sub 2]O[sub 3]), iron sulphide and iron pentacarbonyl. The obtained yields show a dependence with the sulphur content of the coals; the organic sulphur content correlates with the conversion and THF-solubles when Red Mud and iron sulphide are added. In spite of the high hydrogen sulphide partial pressure in the reaction, the addition of other sources of sulphur enhances the percentages in conversion products. 15 refs., 2 figs., 3 tabs.
Microwave-hydrothermal processing was compared with conventional hydrothermal processing in the crystallization of hematite from 1M ferric nitrate and hydroxyapatite from calcium oxide and phosphoric acid. Microwave-hydrothermal processing led to the crystallization of hematite while convention-hydrothermal process led to the crystallization of a mixture of goethite and hematite under the same temperature conditions. Thus the crystallization of hematite which is the stable iron oxide phase at high temperatures has been catalyzed by microwaves. Microwave-hydrothermal processing also led to highly crystalline hydroxyapatite powders compared to the conventional hydrothermal processing which also points to the catalytic role of microwaves. The microwave induced effects may be attributed to the generation of localized high temperatures at the reaction sites which enhance reaction rates.
1,3-Dienes derived from steroidal D-ring C17-ketones undergo Ni(II)-catalyzed hydrovinylation to give 1,2- or 1,4-addition of ethylene. Using finely tuned phosphoramidite ligands it is possible to synthesize either the C20 (R)- or the C20 (S)-derivatives without mutual contamination. The proportion of the 1,4-adduct, which is also formed stereoselectively, can be minimized by optimizing the reaction conditions. Since the two alkenes in the resultant dienes have differing steric demands for many potential reactions, and are ideally juxtaposed for further D-ring functionalization, these intermediates could be useful for the preparation of biologically important compounds such as vitamin D analogs and various antitumor steroidal glycosides.
Poly(ethylene terephthalate) (PET) powder from waste bottles was degraded at atmospheric pressure in 7--13 M nitric acid at 70--100 C for 72 h, to clarify the mechanism of a feed stock recycling process. Terephthalic acid (TPA) and ethylene glycol (EG) were produced by the acid-catalyzed heterogeneous hydrolysis of PET in nitric acid, and the resulting EG was simultaneously oxidized to oxalic acid. The kinetics of the hydrolysis of PET in nitric acid could be explained by a modified shrinking core model of chemical reaction control, in which the effective surface area is proportional to the degree of unreacted PET, affected by the deposition of the product TPA. The apparent rate constant was inversely proportional to particle size and to the concentration of the nitric acid. The activation energy of the reaction was 101.3 kJ/mol.
Wheat leaves can be induced by excision to produce fructans. Fructose residues of newly made oligofructans in leaves labeled in vivo with {sup 14}CO{sub 2} are not equally labeled. We report here on a fructosyl transferase activity in wheat leaves catalyzing the reaction: G{sup *}-F{sup *} + G-F-F = G{sup *}-F{sup *}-F + G-F. This activity, described previously in J. artichoke was attributed to fructan:fructan fructosyl transferase (FFT). The rate of this reaction in vitro is much higher than that of net kestose synthesis by SST. Hence, appearance of labeled 1-kestose from sucrose may not be an accurate measure of SST, but a curious reshuffling of hexoses between pools of 1-kestose and sucrose.
Isopropyl chloroacetate has been synthesized by esterification of chloroacetic acid and isopropanol, using lanthanum dodecyl sulfate (LDDS) as the catalyst. Various factors that affected the esterification have been investigated, such as reaction time, different water-carrying agent and the amount of catalyst. Under the condition of 1.2/1 molar ratio of isopropanol to chloroacetic acid, 1.0% catalyst (molar percent of chloroacetic acid), 2.5 h reaction time, 5 mL cyclohexane as water-carrying agent and reflux temperature, the esterification conversion of isopropyl chloroacetate reaches 98.3%. The catalytic activity of LDDS is almost equal to that of a Bronsted acid. LDDS, as one kind of water-tolerant Lewis acid, is an excellent catalyst compared to the traditional Lewis acid. (author)
The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis-Menten kinetics. A large value of KM (KM=5.01+-0.16 M) is obtained, which indicates that the Rh-solvate complex is the catalyst resting state, which has been observed by high-pressure NMR spectroscopy. DFT calculations on the substrate-catalyst complexes, which are undetectable by experimental means, suggest that the major substrate-catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism...
The effect of neutralizing cations on the secondary reactions of the primary products from CO hydrogenation over ion-exchanged zeolite-supported Ru catalysts was investigated using zeolites with different alkali cations (Li/sup +/, Na/sup +/, K/sup +/, Rb/sup +/, Cs/sup +/). The transformation of olefins (propylene and butene) on the zeolites without the metal, under conditions similar to those used for CO hydrogenation, was also studied in order to understand the effect of the various constituents of the support, i.e., the Broensted acid sites generated during catalyst preparation and the alkali cations, on possible secondary reactions of the primary olefinic products. It was established that secondary acid-catalyzedreactions of these primary products can play a major role in shaping product selectivity during CO hydrogenation over zeolite-supported catalysts. Depending on the concentration and the ...
The purpose of this project was to investigate the feasibility of an antiproton catalyzed fission fragment rocket (FFR). The FFR is characterized by the extraction of fission fragments from the fissile fuel, and the utilization of their kinetic energy for thrust generation. A significant drawback to previous FFR designs was the requirement to maintain a critical nuclear pile as the fission fragment source. The author examined the possibility of replacing the critical pile with a sub-critical pile driven by antiprotons. Recent experiments have revealed that antiprotons stimulate highly energetic fissions in {sup 238}U, with a neutron multiplicity of 13.7 neutrons per fission. This interaction was used as a throttled neutron source. The pile consisted of layers of fissile coated fibers which are designed to allow fission fragments to escape them, where the fragments collide with a fluid. The heated fluid is then ejected from the rocket to provide thrust. The ...
Ethylen and, recently, butadiene can be epoxidized directly with oxygen and for the epoxidation of propylene, the use of heterogeneous transition metals and organic peroxides (Halcon-Process) is the major player. But, beside from those notable exceptions, all other epoxidations, including large ones like the epoxidation of plant oils as PVC-stabilizers (about 200.000 t/year), are carried out with peroxy acids. Because mcpba is far to expensive for most applications, short chain peracids like peracetic acid are used. Being much less stable than mcpba and thus risky handled in large amounts and high concentrations, these peroxy acids were preferably prepared in-situ. However, conventional in-situ formation of peracids has the serious drawback, that a strong acid is necessary to catalyze peroxy acid formation from the carboxylic acid and hydrogen peroxide. The presence of a strong acid in the reaction mixture often results in decreased selectivity ...
In this paper, we used Ca-alginate gel beads coated with polyetheneimine and glutaraldehyde to adsorb Expansum penicillium lipase. The immobilized lipase catalyzed esterification of 1-dodecanol with dodecanoic acid in benzene. The results show that when the concentration of Ca-alginate, polyetheneimine (PEI) and glutaraldehyde is 1%, 6% and 1%, respectively, the activity of the immobilized lipase and the amount of adsorbed protein are the highest. The immobilized lipase is better than the SDS-immobilized lipase. The activity of the immobilized lipase connected by glutaraldehyde is higher than the activity of that without glutaraldehyde. The initial rate of the immobilized lipase and lyophilized lipase powder is 5.9 x 10(2) nmol/min.mgpr and 2.8 x 10(1) nmol/min.mgpr, respectively. After the immobilized lipase catalyzed the esterification reaction at 37 degrees C for about 12 hours, 93.3% of 1-dodecanol was converted to ...
An important advantage of carrying out enzymatic catalysis in organic media is the increased solubility of hydrophobic substrates. This study compares a model lipase catalyzed esterification of cholesterol using vinyl acetate (VA) in two such nontraditional media: high-pressure hexane and supercritical (SCF) ethane. The effect of using one of the reactants (VA) as a cosolvent to increase the solubility of the other reactant (cholesterol) in SCF ethane has been investigated. The thermodynamic activity of water (a(w)) in the reaction media was controlled by the direct addition of the salt hydrate pair Na(4)P(2)O(7)/Na(4)P(2)O(7).10H(2)O. The a(w) of the salt hydrate system is shown to be a function of pressure and its variation over the pressure range 104-173 bar has been estimated. The initial reaction rate in pressurized hexane was found to vary linearly with the cholesterol concentration. The reaction ...
Porcine pancreatic lipase immobilized on celite particles has been employed as a catalyst for the esterification of dodecanol and decanoic acid in a predominantly organic system. Solvent influence on the equilibrium position and on the catalyst activity has been studied using 20 solvents, including aliphatic and aromatic hydrocarbons, ethers, ketones, nitro- and halogenated hydrocarbons, and esters. The equilibrium constant for esterification correlates well with the solubility of water in the organic solvent, which in turn shows a good relationship with a function of Guttman's donor number and the electron pair acceptance index number of the solvent. This may be rationalized in terms of the requirements for solvation of water and of the reactants. The catalyst activity, measured as the initial rate of the esterification reaction, is best correlated as a function of both n-octanol-water partition coefficient (log P) and either the electron pair acceptance index or ...
The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzedreactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)
The change in the concentration of hydrogen peroxide in the course of its decomposition was shown, catalyzed by 0.02 M PbI/sub 2/, 0.03 M CuI, 0.02 M KI, 0.02 M FeSo/sub 4/, 6 M HCl, and 1 M HCL + 2 M H/sub 2/SO/sub 4/ at 25 C. It was suggested that in the process of the catalytic decomposition at the initial stage of the reaction, the formation of an intermediate active species containing positively charged halogen occurs; depending on the oxidative power of the counterion, the relative proportions of the hydrogen peroxide decomposing under the action of either the cation or the anion varied.
The development of 'Green Chemistry' requires new materials to replace the conventional organic chemistry by biological catalysts, to produce fine chemicals in an environmentally friendly manner. Microbial whole cells can be directly used as biocatalysts, providing a simple and cheap methodology since enzyme isolation and purification are avoided. High-density polyethylene (HDPE) is a very stable polymer though it can be activated by gamma radiation to induce grafting. Glycidyl methacrylate was grafted onto macroporous HDPE and PP in the range of 1-6%, proportional to the initial monomer concentration. Grafted polymers were further chemically modified with ethylenediamine to generate a cationic hydrogel of micron-size thickness onto the internal polymer surfaces. Modified polymers were able to immobilize Gram-positive and Gram-negative bacteria that can catalyze a chemical reaction as efficient as free cells do.
During this report period, we have obtained a model of montmorillonite clay, and this model has been of great assistance in visualizing how the chemistry of substrate molecules might be altered as it occurs on the surface of the clay. A stereochemical representation of this montmorillonite model is shown. Of particular significance, this model indicates that hydroxyl groups are located in the center of each siloxane ring on the surface of the montmorillonite clay. These hydroxyl groups might serve to bond substrate molecules to the surface of the clay. The next step in our systematic examination of the radical cation-initiated dimerization of plant monomers from the C{sub 6}-C{sub 3} pool of shikimic acid metabolites was to study the dimerization of cinnamic acid and its derivatives. In the next block of research, we examined the reaction of montmorillonite clay (K-10) with methyleugenol. 2 refs.
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...
The objective of this work is to improve the process for CO{sub 2} capture by alkanolamine absorption/stripping by developing an alternative solvent, aqueous K{sub 2}CO{sub 3} promoted by piperazine. Thermodynamic modeling predicts that the heat of desorption of CO{sub 2} from 5m K+/2.5 PZ from 85 kJ/mole at 40 C to 30 kJ/mole at 120 C. Mass transfer modeling of this solvent suggests that carbonate and general salt concentration play a major role in catalyzing the rate of reaction of CO{sub 2} with piperazine. Stripper modeling suggests that with the multipressure stripper, the energy consumption with a generic solvent decreases by 15% as the heat of desorption is decreased from 23.8 to 18.5 kcal/gmol. A second pilot plant campaign with 5m K+/2.5 PZ was successfully completed.
In this paper nickel acetate catalyzed sodium borohydride cartridges have been prepared and hydrolyzed with water for hydrogen production. Two technological solutions have been tested to increase the overall hydrogen yield, namely a porous water diffuser and a hydrophobic membrane. The first was used to improve water diffusion inside the hydride while the second to confine water inside the cartridge. The generated hydrogen flow showed a very reproducible behavior. Hydrogen promptly evolved just after water was pumped into the cartridge. After some initial peaks, a constant hydrogen flow has been recorded for the whole reaction time. The constant flow was related to the presence of the porous diffuser. The use of a hydrophobic membrane to confine the water inside the cartridge allowed to increase the overall hydrogen yield: about 6 water molecules per mol of hydride were required to complete the reaction. The ...
The exchange of Eu[sup 3+] for Na[sup +] cations into the sodalite cages of X zeolite (Eu[sub 25]Na[sub 11]X) leads selectively to the isomerization reaction of cyclopropane to propylene. The latter reaction is catalyzed by Broensted acid sites with an apparent activation energy of 10.6 kcal/mol. Sorption measurements of cyclopropane and propylene with Eu/NaX and NaX zeolites at 40 C support the view that Na[sup +] cations might be considered as sites for sorption of these molecules. Force fields created by Eu[sub 4]O[sup 10+] present in Eu/NaX zeolite may affect sorption. On the other hand, Broensted acid sites in Eu/NaX enhance sorption of cyclopropane and propylene at 40 C. Chemisorption of propylene on the Broensted acid sites of Eu/NaX is reversible and may occur via a propylene carbenium cation intermediate. Small amounts of hexene are formed during this sorption. The amount of Broensted acid sites in the present ...
Three abiotic systems are described that catalyze the reductive dehalogenation of heavily halogenated environmental pollutants, including carbon tetrachloride, trichloroethene, and perchloroethene. These systems include (a) an electrolytic reactor in which the potential on the working electrode (cathode) is fixed by using a potentiostat, (b) a light-driven system consisting of a semiconductor and (covalently attached) macrocycle that can accept light transmitted via an optical fiber, and a light-driven, two-solvent (isopropanol/acetone) system that promotes dehalogenation reactions via an unknown mechanism. Each is capable of accelerating reductive dehalogenation reactions to very high rates under laboratory conditions. Typically, millimolar concentrations of aqueous-phase targets can be dehalogenated in minutes to hours. The description of each system includes the elements of reaction mechanism (to the ...
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. Oxide catalysis can be a complex process with both metal cation and oxygen ...
The carbothermal reduction of clay minerals in a nitrogen atmosphere is a well established method for producing #beta#'-sialon. There has been some debate within the literature concerning the role that Fe plays in the formation of the #beta#'-sialon phase. However, most workers accept that Fe is able to either catalyze or promote the formation of #beta#'-sialon although some workers have indicated that the function of the Fe is controlled by gas flow rate and there is evidence that Fe also promotes formation of additional phases. The aim of the present study was to characterize the behaviour of Fe within the #beta#'-sialon synthesis. "5"7Fe Moessbauer spectroscopy was employed for the study because this technique is specific to Fe and does not suffer interference from other elements. Moreover, both the coordination and oxidation state and the relative abundances of the various Fe-containing phases are able to be monitored. A previous Moessbauer study of Fe in ...
The objectives of this project are to develop feasible synthetic routes to produce (1) 4(4{prime}-hydroxy-5{prime},6{prime},7{prime},8{prime}-tetrahydro-1{prime}-naphthylmethyl)-6-methyldibenzothiophene, and (2) a 1-hydroxynaphthalene-dibenzothiophene polymer. These compounds are thought to be representative of sulfur containing molecules in coal. The program is divided into three tasks, the first of which is a project work plan that has already been submitted. There are several possible synthetic routes to the target molecule (1). The authors are now investigating two general synthetic approaches: coupling of a dialkylated dibenzothiophene fragment with the phenol, and coupling of a monoalkylated dibenzothiophene fragment with a monoalkylated phenol fragment. This quarter they developed syntheses for the reaction fragments and conducted some preliminary coupling experiments. They found that polymerization of the fragments is a problem; however, using an acidic ...
It is well established from experiments in premixed, laminar flames, jet-stirred reactors, flow reactors, and batch reactors that SO2 acts to catalyze hydrogen atom removal at stoichiometric and reducing conditions. However, the commonly accepted mechanism for radical removal, SO2 + H(+M) reversible arrow HOSO(+M), HOSO + H/OH reversible arrow SO2 + H-2/H2O, has been challenged by recent theoretical and experimental results. Based on ab initio calculations for key reactions, we update the kinetic model for this chemistry and re-examine the mechanism of fuel/SO2 interactions. We find that the interaction of SO, with the radical pool is more complex than previously assumed, involving HOSO and SO, as well as, at high temperatures also HSO, SH, and S. The revised mechanism with a high rate constant for H + SO2 recombination and with SO + H2O, rather than SO2 + H-2, as major products of the HOSO + H reaction is in agreement with ...
Ionic liquids can enhance the activity, selectivity, and stability of enzyme catalysts. Enzymes and ionic liquids as catalysts are seen as a more environmentally friendly technology than the use of traditional catalyst materials in biofuels production. This study investigated the lipase catalyzed esterification reaction for biodiesel production in the presence of the ionic liquid BMIM PF{sub 6}. Methyl acetate was used as the acyl acceptor. A titremetric assay was conducted to measure the activity of the lipase with various amounts of ionic liquid. Reaction parameters were investigated in order to determine their effects on biodiesel conversion. An 80 per cent overall methyl oleate biodiesel yield was successfully produced in the presence of the ionic liquid. The ionic liquid improved lipase activity as well as overall biodiesel yield. Results also showed that the addition of the ionic liquid facilitated the separation of ...
A calorimetric microliter plate assay for ethanol amplified by aldehyde dehydrogenase (ALDH) was developed. In the assay ethanol from a sample took part in a chain-reactioncatalyzed by alcohol dehydrogenase (ADH) and amplified by ALDH in the presence of NAD{sup +}, diaphorase, and p-ibdonitrotetrazolium-violet (INT-violet)(a precursor of red product). The resultant reaction gave a red color, the intensity of which was proportional to the amount of ethanol present. Using the technique, the content of activity from peanuts of differing maturity and curing stages were determined respectively. Data showed that immature peanuts had a higher level of ethanol and a lower ADH activity than mature peanuts, and that the level of ethanol and ADH activity decreased with the curing time. This indicates that peanut maturity and curing have an effect on ethanol. Also, this implies that other peanut volatiles could be affected in the same ...
Improvement in efficiency and profitability of hydrogenation reaction of heavy hydrocarbon resources is the most important matter to be done. In this study, coprocessing of coal and heavy oil vacuum residue was conducted using syngas-water as a hydrogen source. For the investigation of effect of the reaction temperature during the coprocessing of Wandoan coal and Arabian heavy vacuum residue using Fe(CO)5 as a catalyst, the conversion, 66.0% was obtained at 425{degree}C. For the investigation of effect of reaction time, the yield of light fractions further increased during the two stage reaction at 400{degree}C for 60 minutes and at 425{degree}C for 60 minutes. Finally, almost 100% of THF-soluble matter was obtained through the reaction using 2 mmol of Fe(CO)5 catalyst at 400{degree}C for 60 minutes, and hydrogenation of heavy oil was proceeded simultaneously. When comparing ...
Lipase catalyzed esterification reactions between lactic acid and several fatty acids have been studied. Difficulties arise in esterifying lactic acid because of the potential for this substance to act both as an acyl donor and as a nucleophile. These difficulties were minimized via strategies which greatly increased the yield of the desired ester. Use of the companion fatty acid in excess with respect to lactic acid in an apolar solvent (n-hexane) in which the lactic is not completely dissolved has been employed to minimize the potential for lactic acid to act as an acyl donor in a self-polymerization reaction.Beneficial and sinergistic effects of both silica gel and molecular sieves on conversion to the desired product are described. However, careful control of the amount of molecular sieves used is required. This fact is a consequence of two opposing effects of this material: i.e. adsorption of both lactic acid and water ...
["3H]Indole-3-acetyl-myo-inositol was hydrolyzed by buffered extracts of acetone powders prepared from 4 day shoots of dark grown Zea mays L. seedlings. The hydrolytic activity was proportional to the amount of extract added and was linear for up to 6 hours at 37"0C. Boiled or alcohol denatured extracts were inactive. Analysis of reaction mixtures by high performance liquid chromatography demonstrated that not all isomers of indole-3-acetyl-myo-inositol were hydrolyzed at the same rate. Buffered extracts of acetone powders were prepared from coleoptiles and mesocotyls. The rates of hydrolysis observed with coleoptile extracts were greater than those observed with mesocotyl extracts. Active extracts also catalyzed the hydrolysis of esterase substrates such as #alpha#-naphthyl acetate and the methyl esters of indoleacetic acid and naphthyleneacetic acid. Attempts to purify the indole-3-acetyl-myo-inositol hydrolyzing activity by chromatographic ...
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
Reversible protein glutathionylation plays a key role in cellular regulation and cell signaling and protects protein thiols from hyperoxidation. Sulfiredoxin (Srx), an enzyme that catalyzes the reduction...Full Text Available
New palladium(II) complexes (2), bearing NHC/TPPTS ligands, (NHC=benzimidazol-2-ylidene; TPPTS=triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt) have been prepared and characterized by elemental analyses and spectroscopic methods. Their ability to catalyze the Suzuki-Miyaura reaction in neat water has been studied at 100^oC. Very high activities have been observed in the coupling of phenylboronic acid with aryl chlorides in the presence of 1% of the catalyst. We have compared the electronic properties of cis-[PdBr2(NHC)(TPPTS)] with the related complexes, [PdX2(NHC)]2 and [trans-PdBr2(NHC)(pdca)] (pdca=pyridine-2,6-dicarboxyic acid) (3) via three different techniques: cyclic voltammetry, thermogravimetric analysis and ^1^3C NMR spectroscopy.
Sucrose phosphate synthase (SPS) catalyzes the transfer of a glycosyl group from an activated donor sugar, such as uridine diphosphate glucose (UDP-Glc), to a saccharide acceptor D-fructose 6-phosphate (F6P), resulting in the formation of UDP and D-sucrose-6'-phosphate (S6P). This is a central regulatory process in the production of sucrose in plants, cyanobacteria, and proteobacteria. Here, we report the crystal structure of SPS from the nonphotosynthetic bacterium Halothermothrix orenii and its complexes with the substrate F6P and the product S6P. SPS has two distinct Rossmann-fold domains with a large substrate binding cleft at the interdomain interface. Structures of two complexes show that both the substrate F6P and the product S6P bind to the A-domain of SPS. Based on comparative analysis of the SPS structure with other related enzymes, the donor substrate, nucleotide diphosphate glucose, binds to the B-domain of SPS. Furthermore, we propose a ...
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...
A novel bioelectrochemical membrane reactor (BEMR), which takes advantage of a membrane bioreactor (MBR) and microbial fuel cells (MFC), is developed for wastewater treatment and energy recovery. In this system, stainless steel mesh with biofilm formed on it serves as both the cathode and the filtration material. Oxygen reduction reactions are effectively catalyzed by the microorganisms attached on the mesh. The effluent turbidity from the BEMR system was low during most of the operation period, and the chemical oxygen demand and NH(4)(+)-N removal efficiencies averaged 92.4% and 95.6%, respectively. With an increase in hydraulic retention time and a decrease in loading rate, the system performance was enhanced. In this BEMR process, a maximum power density of 4.35 W/m(3) and a current density of 18.32 A/m(3) were obtained at a hydraulic retention time of 150 min and external resister of 100 ?. The Coulombic efficiency was 8.2%. Though the ...
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 is often the main degradation product, has ...
Badger (Cambridge, MA) and Mobil (Fairfax, VA) are ready to jointly license a new cumene technology that they say achieves higher yields and product purity than existing processes. The zeolite-based technology is scheduled to be introduced at next month's DeWitt Petrochemical Review in Houston. The Mobil/Badger technology aims to challenge the dominant position of UOP's (Des Plaines, IL) solid phosphoric acid (SPA) catalyst process - which accounts for 80%-90% of the world's cumene production. In addition, Monsanto/Kellogg's aluminum chloride-based technology has gained significant momentum since its introduction in the 1980s. And late last year, ABB Lummus Crest (Bloomfield, NJ) also began marketing a zeolite-based cumene technology. While all the technologies make cumene via the alkylation of benzene with propylene, the Mobil/Badger process uses a zeolite-containing catalyst designed by Mobil to selectively catalyze the ...
Lipase catalyzed esterification of therapeutic drugs to functional self-assembled monolayers (SAMs) on 316L stainless steel (SS) after assembly has been demonstrated. SAMs of 16-mercaptohexadecanoic acid (-COOH SAM) and 11-mercapto-1-undecanol (-OH SAM) were formed on 316L SS, and lipase catalysis was used to attach therapeutic drugs, perphenazine and ibuprofen, respectively, on these SAMs. The reaction was carried out in toluene at 60 degrees C for 5 h using Novozyme-435 as the biocatalyst. The FTIR spectra after surface modification of -OH SAMs showed the presence of the C=O stretching bands at 1745 cm(-1), which was absent in the FTIR spectra of -OH SAMs. Similarly, the FTIR spectra after the reaction of the -COOH SAM with perphenazine showed two peaks in the carbonyl region, a peak at 1764 cm(-1), which is the representative peak for the C=O stretching for esters. The second peak at 1681 cm(-1) is assigned to the C=O ...
This work proposes an innovative blend of potassium carbonate (K{sub 2}CO{sub 3}) and piperazine (PZ) as a solvent for CO{sub 2} removal from combustion flue gas in an absorber/stripper. The equilibrium partial pressure and the rate of absorption of CO{sub 2} were measured in a wetted-wall column in 0.0 to 6.2 m K{sup +} and 0.6 to 3.6 m PZ at 25 to 110 C. The equilibrium speciation of the solution was determined by {sup 1}H NMR under similar conditions. A rigorous thermodynamic model, based on electrolyte non-random two-liquid (ENRTL) theory, was developed to represent equilibrium behavior. A rate model was developed to describe the absorption rate by integration of eddy diffusivity theory with complex kinetics. Both models were used to explain behavior in terms of equilibrium constants, activity coefficients, and rate constants. The addition of potassium to the amine increases the concentration of CO{sub 3}{sup 2-}/HCO{sub 3}{sup -} in solution. The buffer reduces protonation of the ...
A general palladium-catalyzed carbonylative Sonogashira coupling of benzyl chlorides with terminal acetylenes has been established. Depending on the alkyne 1,4-diaryl-3-butyn-2-ones or substituted furanones are obtained in moderate to good yields. Best catalytic performance is achieved applying a mixed Pd(PPh(3))Cl(2)/P(OPh)(3) catalyst system. PMID:21968528
(methine-{sup 3}H)1,1-Di-(4-chlorophenyl)-2,2,2-trichloroethane ((methine-{sup 3}H)DDT) and its di-(4-nitrophenyl) analog, both of high purity with a moderately high specific activity were prepared. Chloro-benzene was condensed with (1-{sup 3}H)1-(4-chlorophenyl)-2,2,2-trichloro-ethanol, which has been synthesized by sodium boro({sup 3}H)hydride reduction of 4-chlorophenyl trichloromethyl ketone. The purified ({sup 3}H)DDT had a specific activity of 0.77 Ci/mmol (28.49 GBq/mmol). (methine-{sup 3}H)1,1-Diphenyl-2,2,2-trichloroethane was similarly synthesized and was nitrated to give (methine-{sup 3}H)1,1-di-(4-nitrophenyl)-2,2,2-trichloro-ethane of 1.63 Ci/mmol (60.31 GBq/mmol). Dehydrochlorination with housefly enzyme (glutathione-dependent DDT dehydrochlorinase) showed a remarkable isotope effect. For DDT, the observed tritium isotope effect on V{sub max}/K{sub m} was 11.51{plus minus}0.52. For the nitro-analog, the value was 11.3{plus minus}1.2. We measured deuterium isotope effect ...
Trihydroxynaphthalene reductase catalyzes two intermediate steps in the fungal melanin biosynthetic pathway. The enzyme, a typical short-chain dehydrogenase, is the biochemical target of three commercial fungicides. The fungicides bind preferentially to the NADPH form of the enzyme. Three X-ray structures of the Magnaporthe grisea enzyme complexed with NADPH and two commercial and one experimental fungicide were determined at 1.7 {angstrom} (pyroquilon), 2.0 {angstrom} (2,3-dihydro-4-nitro-1H-inden-1-one, 1), and 2.1 {angstrom} (phthalide) resolutions. The chemically distinct inhibitors occupy similar space within the enzyme's active site. The three inhibitors share hydrogen bonds with the side chain hydroxyls of Ser-164 and Tyr-178 via a carbonyl oxygen (pyroquilon and 1) or via a carbonyl oxygen and a ring oxygen (phthalide). Active site residues occupy similar positions among the three structures. A buried water molecule that is hydrogen bonded to the ...
Under appropriate conditions, bismuth molybdates can catalyze a number of transformations of olefins with selective oxidation being of particular importance. Experimental evidence suggests that the propylene is activated to an allylic species by a site associated with the Bi and that the oxidation step occurs at an Mo site. In order to address the mechanistic steps associated with these Mo sites. The authors discuss the chemistry of terminal oxo and imido groups. They find that for surface sites such as 1 about, 2 about and 3 about, the presence of two double bonds leads to a much more active species than those with a single multiple bond. This leads to a situation similar to that in olefin metathesis by high oxidation state Mo catalysis where the (spectator) oxo group species promotes formation of the metallacycle intermediate by formation of a partial Mo==O triple bond that stabilizes the intermediate. Calculations suggest that the magnitude of the spectator oxo ...
Cholera toxin catalyzes transfer of radiolabel from ["3"2P]NAD"+ to several peptides in particulate preparations of human foreskin fibroblasts. Resolution of these peptides by two-dimensional gel electrophoresis allowed identification of two peptides of M/sub r/ = 42,000 and 52,000 as peptide subunits of a regulatory component of adenylate cyclase. The radiolabeling of another group of peptides (M/sub r/ = 50,000 to 65,000) suggested that cholera toxin could catalyze ADP-ribosylation of cytoskeletal proteins. This suggestion was confirmed by showing that incubation with cholera toxin and ["3"2P]NAD"+ caused radiolabeling of purified microtubule and intermediate filament proteins.
Many bacteria, both gram positive and gram negative, extrude in an energy-dependent manner the fluorescent pH indicator 2',7'-bis-(2-carboxyethyl)-5[and -6]-carboxyfluorescein (BCECF) (D. Molenaar,...Full Text Available
We recently identified a cDNA encoding a putative isovaleryl-coenzyme A (CoA) dehydrogenase in Arabidopsis (AtIVD). In animals, this homotetrameric enzyme is located in mitochondria and catalyzes the...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
Phospho-beta-galactosidase (P-beta-gal), the enzyme which catalyzes the first step in the metabolism of intracellular lactose phosphate, occurred at high specific activity in the cytoplasm in 12 of...Full Text Available
The speA gene in Bacillus subtilis encodes arginine decarboxylase, which catalyzes the conversion of arginine to agmatine. Arginine decarboxylase is an important enzyme...Full Text Available
During the past decade elevated phospholipase D (PLD) activity has been reported in virtually all cancers where it has been examined. PLD catalyzes the hydrolysis of phosphatidylcholine to generate...Full Text Available
Phenylketonuria (PKU) is a common genetic disorder in humans that arises from deficient activity of phenylalanine hydroxylase (PAH), which catalyzes the conversion of phenylalanine to tyrosine....Full Text Available
AIM:N-acetyltransferase 2 (NAT2) is an important enzyme catalyzing N-acetylation of sulfasalazine (SASP). The aim of the present study was to investigate...Full Text Available
Combined QM(PM3)/MM molecular dynamics simulations together with QM(DFT)/MM optimizations for key configurations have been performed to elucidate the enzymatic catalysis mechanism on the detoxification...Full Text Available
As part of the study of cytokinin metabolic pathways, an enzyme, adenosine phosphorylase (EC 2.4.2.-), which catalyzed the ribosylation of N6-(Δ2-isopentenyl)adenine,...Full Text Available
BackgroundThe immunoregulatory enzyme indoleamine 2,3-dioxygenase, which catalyzes the conversion of tryptophan into kynurenine, is expressed in a significant subset of patients...Full Text Available
Alkyl halides react rapidly with purines and pyrimidines in the presence of fluoride ion. Alkylation of thymidine leads to novel dimeric nucleoside derivatives bridged through N3. Alkylation of thymidine...Full Text Available
BackgroundCyclooxygenase (cox) is the rate-limiting enzyme, which catalyzes the conversion of arachidonic acid into prostaglandins and contributes to the inflammatory process. Cyclooxygenase-2...Full Text Available
Mice lacking acyl-CoA:diacylglycerol acyltransferase 1 (DGAT1), an enzyme that catalyzes the terminal step in triacylglycerol synthesis, have enhanced insulin sensitivity and are protected from...Full Text Available
A cell-free system which catalyzes the biosynthesis of terpene hydrocarbons when supplemented with mevalonate, Mn2+, and ATP was prepared from the scutellum-embryonic axis region of maize...Full Text Available
BackgroundWax esters are important ingredients in cosmetics, pharmaceuticals, lubricants and other chemical industries due to their excellent wetting property. Since the naturally...Full Text Available
Under anaerobic conditions, several species of green algae perform a light-dependent hydrogen production catalyzed by a special group of [FeFe] hydrogenases termed HydA. Although highly interesting...Full Text Available
Social support is a critical, yet underutilized resource when undergoing cancer care. Underutilization occurs in two conditions: (a) when patients fail to seek out information, material assistance,...Full Text Available
NAD(P)H:rubredoxin oxidoreductase (NROR) has been purified from the hyperthermophilic archaeon Pyrococcus furiosus. The enzyme is exceedingly active in catalyzing the NADPH-dependent...Full Text Available
Lipase from Pseudomonas fragi 22.39B was modified with polyethylene glycol. The modified lipase (PEG-lipase) was soluble and active in organic solvents such as benzene and 1,1,1-trichloroethane. PEG-lipase catalyzed esterification of chiral secondary alcohols with fatty acids in benzene and exhibited preference for R isomers over S isomers. Km and Vmax values for each isomer of various alcohols were obtained by kinetic study of the esterification in benzene. PEG-lipase-catalyzed esterification leads to optical resolution of a racemic alcohol. PMID:2635854
Various MLM-type (M, medium-chain fatty acids; L, long-chain fatty acids) structured triacylglycerols were produced in pilot- or small-scale packed-bed reactors by lipase-catalyzed acidolysis. The incorporation and acyl migration of octanoic acid were measured by gas chromatography and Grignard degradation, and ranged from 39.0 to 48.7% and 0.6 to 9.3%, respectively. Quantitation of triacylglycerol molecular species was performed by ammonia negative ion chemical ionization (NICI) mass spectrometry (MS). The proportion of ACN (acyl carbon number) 34 species that contained one C-18 fatty acid and two C-8:0, in samples analyzed, varied from 12.5 to 23.2%. The selected regioisomers MLM and MML within the ACN 34 species group were quantified by NICI tandem MS (MS/MS) and were in the range of 97.1 to 98.4% and 1.6 to 2.9%, respectively. There was no correlation between the level of acyl migration during lipase-catalyzed esterification and the level ...
Only 15mol% of l-proline in ethanol proved to be a very efficient catalyst for the one-pot synthesis of a wide variety of highly substituted pyridines at room temperature. The methodology is mild, efficient, high yielding, and the products can be directly recrystallized from hot ethanol.
The hepatic removal of albumin-bound substances from plasma requires that they dissociate from albumin. Using indirect methods, we and others have proposed that dissociation may be catalyzed by interaction...Full Text Available
Type II NAD(P)H:quinone oxidoreductases (NDH-2) catalyze the two-electron transfer from NAD(P)H to quinones, without any energy-transducing site. NDH-2 accomplish the turnover of NAD(P)H, regenerating...Full Text Available
Several cDNA clones encoding Δ1-pyrroline-5-carboxylate reductase (P5CR, l-proline:NAD[P]+ 5-oxidoreductase, EC 1.5.1.2), which catalyzes the terminal step in...Full Text Available
At the RIKEN-RAL Muon Facility, ?- to ? sticking K? X-rays were observed for the first time taking advantage of the pulsed beam structure. The precision of the present measurements was insufficient to distinguish between theoretical models, however the observed K?/K? X-ray intensity ratio tends to be smaller than most of these theoretical predictions.
AOT reverse micelles are used to cosolubilize hydrophilic and hydrophobic reactants of lipase catalysed esterification. Depending on the nature of the alcohol, a drastic change of the initial rate of the esterification is observed. A structural study of the micellar system with and without reactant is undertaken to explain the change in the activity with the various alcohols. PMID:7832997
Acyl-CoA:diacylglycerol acyltransferase (EC 2.3.1.20) is a membrane protein present mainly in the endoplasmic reticulum. It catalyzes the final and committed step in the biosynthesis of triacylglycerol,...Full Text Available
Sphingomonas paucimobilis B90A contains two variants, LinA1 and LinA2, of a dehydrochlorinase that catalyzes the first and second steps in the metabolism of hexachlorocyclohexanes (R....Full Text Available
Data on the reactions of thiocyanogen and thiocyanogen halides with unsaturated compounds are systematised. The kinetic and stereo- and regiochemical regularities of these reactions are analysed. The bibliography includes 81 references.
The problem of homochirality is of crucial importance for the origins of Life. While most laboratory studies are focused on the search of physical and chemical sources of handedness in the Universe, they reflect only one aspect of the problem: the origin of homochiral biomolecules. At the same time, any space environments where biomolecules are expected to form and where they have to pass through before the first primitive forms of Life emerge, include strong irradiation or/and high temperatures. This automatically implies the possibility of losing the optical activity, i.e. racemization. The simulation experiments performed by our group deal with the following two aspects of amino acid abiotic chemistry: (1) amino acid pyrolysis associated with their extraterrestrial delivery; and (2) peptide formation from amino acids catalyzed by inorganic oxides. According to our observations, the racemization phenomena are very common in the systems considered, not only under ...
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.
Nine coals from Spanish, British, German and American mining basins were hydrogenated using Fe catalyst precursors (red mud and FeSO{sub 4}), without solvent at 300, 350, and 400 {degree}C and 10 MPa of H{sub 2}. Overall conversion and product distribution are related to the textural characteristics of the original coals and are studies throughout the distinct hydrogenation processes. Results reveal that with FeSO{sub 4} as a catalyst precursor, conversions increase with coal surface area. However, when red mud (RM) is used, conversions are independent of coal textural characteristics. Higher conversions are obtained with FeSO{sub 4} than with RM at 300 and 350 {degree}C whereas at 400 {degree}C higher conversions are obtained with RM. This different catalytic activity is also reflected in the changes of the textural characteristics observed in each case. Up to 350 {degree}C, the residues from FeSO{sub 4}-catalyzed processes reveal increased microporosity ...
Previous research has characterized insight as the product of internal processes, and has thus investigated the cognitive and motivational processes that immediately precede it. In this research, however, we investigate whether insight can be catalyzed by a cultural artifact, an external object imbued with learned meaning. Specifically, we exposed participants to an illuminating lightbulb - an iconic image of insight - prior to or during insight problem-solving. Across four studies, exposing participants to an illuminating lightbulb primed concepts associated with achieving an insight, and enhanced insight problem-solving in three different domains (spatial, verbal, and mathematical), but did not enhance general (non-insight) problem-solving.
A catalytic trap oxidizer based on a radial flow metal mesh filter was developed for use as an after treatment device on light-duty diesel vehicles. A complete system for assisted regeneration was devised to enable this unit to operate without blocking during all normal driving modes. The integration of the catalyzed trap and regeneration system with the vehicle to provide a practical system for the reduction of diesel particulate emissions is discussed. To date, many prototype catalytic trap and regeneration system installations have been completed on various test vehicles, both naturally aspirated and turbocharged. The operational conditions and test results from a selection of these studies are presented.
The vacuum polarization splitting of the M-shell states in muonic hydrogen can have a profound influence on the muonit de-excitation cascade in deuterium and tritium targets. The cascade also shows sensitive dependence on the precise rate of transfer processes between certain excited muonic deuterium and tritium atoms. Recent experimental data, where a much greater population of the (d..mu..) qs state (1/sub 1//sub //sub s/) was found than previously predicted, can be explained if the transfer rates from the (d..mu..) M-shell are assumed to be strongly suppressed.
We investigate, from a spacetime perspective, some aspects of Horowitz's recent conjecture that black strings may catalyze the decay of Kaluza-Klein spacetimes into a bubble of nothing. We identify classical configurations that interpolate between flat space and the bubble, and discuss the energetics of the transition. We investigate the effects of winding tachyons on the size and shape of the barrier and find no evidence at large compactification radius that tachyons enhance the tunneling rate. For the interesting radii, of order the string scale, the question is difficult to answer due to the failure of the {alpha}' expansion.
At the RIKEN-RAL Muon Facility, {mu}{sup -} to {alpha} sticking K{sub {beta}} X-rays were observed for the first time taking advantage of the pulsed beam structure. The precision of the present measurements was insufficient to distinguish between theoretical models, however the observed K{sub {beta}}/K{sub {alpha}} X-ray intensity ratio tends to be smaller than most of these theoretical predictions.
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...
For the development of a rechargeable zinc/air battery, La{sub 0.6}Ca{sub 0.4}CoO{sub 3}-catalyzed (perovskite) bifunctional oxygen electrodes and pasted zinc electrodes were prepared and tested in monopolar zinc/air cells. The cells were cycled in moderately alkaline electrolyte. The maximum power as well as the cycle life of the cells were investigated. Up to 450 cycles could be reached, and attractive specific energies and powers were obtained. (author) 3 figs., 4 refs.
The review covers the development within the field of cleavable surfactants since 2003. Cleavable surfactants are amphiphiles in which a weak linkage has been deliberately inserted, normally, but not always, between the hydrophobic tail and the polar headgroup. Alkali labile linkages that have been used for the purpose include normal ester bonds, betaine esters, and carbonates. Ketals and ortho esters are example of bonds that are susceptible to acid hydrolysis. Several investigations deal with cationic ester-containing surfactants, both monomeric and dimeric species, the latter being gemini surfactants. Ester, amide and carbonate containing surfactants have been investigated with respect to enzyme catalyzed hydrolysis. The main incentive for the development of novel cleavable surfactants ...
An experiment has been performed to investigate the chemical reaction between the liquid phases of the eutectic lithium-lead (Li/sub 17/Pb/sub 83/) and water. The reactants and products were constrained within a closed reaction vessel, allowing the extent of reaction to be determined from the partial pressure of the hydrogen reaction product. The data from the tests showed that the extent of reaction did not depend upon the water temperature. The data also indicated that the extent of reaction passed through a maximum as the initial liquid metal temperature was varied from 350 to 500 C, and a model was developed to explain this behavior. 11 refs., 3 figs.
Semiclassical analysis of heavy ion induced transfer reactions are discussed for the quasielastic region. Some unique aspects of these reactions are shown, the variety of features which can be understood semiclassically is demonstrated, and some open problems are indicated. 28 refs., 16 figs. (LEW)
The shrinking core model is examined for gas-solid noncatalytic reactions with a self-inhibited rate form and it is shown that multiple reaction pathways are possible for solid particles reacted under identical conditions. The observed reaction rate can have up to two discontinuities (jumps) during reaction for particles of spherical and cylindrical shape. The geometric instability analysis reveals that the reaction interface is stable under a very limited set of conditions only for solid particles of slab geometry. For a sphere or cylinder at large Biot numbers the reaction interface is always potentially unstable. This model provides a plausible explanation for gas-solid reactions which exhibit erratic shrinking core behavior.
The effects of temperatures, durations of treatment, and derivations from spermatophores or spermaries on in vitro acrosome reaction of the spermatozoa in the Chinese mitten crab Eriocheir sinensis...Full Text Available
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.
Atmospheric pressure tests were performed in which a palladium catalyst ignites and stabilizes the homogeneous combustion of methane. Palladium exhibited a reversible deactivation at temperatures above 750 C, which acted to ``self-regulate`` its operating temperature. A properly treated palladium catalyst could be employed to preheat a methane/air mixture to temperatures required for ignition of gaseous combustion (ca. 800 C) without itself being exposed to the mixture adiabatic flame temperature. The operating temperature of the palladium was found to be relatively insensitive to the methane fuel concentration or catalyst inlet temperature over a wide range of conditions. Thus, palladium is well suited for application in the ignition and stabilization of methane combustion.
A series of [60]fullerene-substituted phenylalanine (Baa) and lysine derivatives have been prepared by the condensation of 1,2-(4prime-oxocyclohexano)fullerene with the appropriately protected (4-amino)phenylalanine and lysine, respectively. Conversion of the imine to the corresponding amine is achieved by di-acid catalyzed hydroboration. The reduction of the imine is not accompanied by hydroboration of the fullerene cage. The [70]fullerene phenylalanine derivative has also been prepared as have the di-amino acid derivatives. The compounds were characterized by MALDI-TOF mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry. 1H and 13C NMR spectroscopy allowed the observation of diastereomers. Fullerene-substituted peptides may be synthesized on relatively large scale by solid-pha...
During this reporting period two direct coal liquefaction experiments have been completed and a third is underway. These experiments have produced conversion and selectivity data on samples of Alabama bituminous coal slurried in tetralin and catalyzed using iron-titanium hydride. The experiments address the liquefaction of an agglomerating coal. Conversions of 45 to 55% DAF in 30 min have been recorded at 500/sup 0/F and 520 psia. Equipment modifications were made in an attempt to eliminate the problem of alloy binding in the hydride formation vessel. 4 figs., 4 tabs.
For the development of a rechargeable zinc/air battery, La[sub 0.6]Ca[sub 0.4]CoO[sub 3]-catalyzed (perovskite) bifunctional oxygen electrodes and pasted zinc electrodes were prepared and tested in monopolar zinc/air cells. In addition, a bipolar Zn/air stack was tested using reticulated copper foam as substrate for the zinc deposit. The cells were cycled in moderately alkaline ZnO-saturated electrolyte with KF as an electrolyte additive. The maximum power as well as the cycle life of the cells was investigated. The differences in porosity of the zinc electrode before and after the long-term test were analyzed using mercury porosimetry. (author) 8 figs., 13 refs.
Stimulated bremsstrahlung in an undulating electric field in the lasing beam direction (electric wiggler) was shown to be possible from the quantum- mechanical viewpoint. Herein, this possibility is scrutinized from the viewpoint of classical electrodynamics. It is found that if stimulated bremsstrahlung in a transverse undulating magnetic field (magnetic wiggler) occurs, stimulated bremsstrahlung in the electric wiggler must also occur. We further show that a free electron laser (FEL) using a magnetic wiggler to provide a catalyzer field for stimulated bremsstrahlung cannot serve as a practical FEL operating in the soft x-ray region from both theoretical and experimental viewpoints. On the other hand, the authors demonstrate that the FEL using a traveling wake field in a two-beam elliptical pill-box cavity is well suited as a source of coherent radiation in the soft x-ray region.
Uridine phosphorylase (UPP) catalyzes the reversible conversion of uridine to uracil and ribose-1-phosphate and plays an important pharmacological role in activating fluoropyrimidine nucleoside chemotherapeutic agents such as 5-fluorouracil and capecitabine. Most vertebrate animals, including humans, possess two homologs of this enzyme (UPP1 & UPP2), of which UPP1 has been more thoroughly studied and is better characterized. Here, we report two crystallographic structures of human UPP2 (hUPP2) in distinctly active and inactive conformations. These structures reveal that a conditional intramolecular disulfide bridge can form within the protein that dislocates a critical phosphate-coordinating arginine residue (R100) away from the active site, disabling the enzyme. In vitro activity measurem...
The chemical reaction between nitric acid and sodium chloride was investigated in onder to provide preliminary information for subsequent studies on the interaction between simulated Purex waste solution and salt. The reaction is characterized by the production of chlorine and nitrosyl chloride and can be considered to be the same as the aqua regia reaction. Within the limits of the conditions imposed by the projected field studies, the acid concentration and temperature are the two parameters which control the extent of the interaction. (auth)
Synthesis of silver nanoparticles based on a polyol process and variable frequency microwave (VFM) was investigated. Comparing to a thermal method, the reaction by VFM radiation was much faster. The effects of silver nitrate concentration, poly(N-vinylpyrrolidone) (PVP) concentration, reaction time and reaction temperature were studied. It was found that the higher concentration of silver nitrate, longer reaction time and higher temperature increased the particle size while the higher concentration of PVP decreased the particle size.
We have developed a set of modeled nuclear reaction cross sections for use in radiochemical diagnostics. Systematics for the input parameters required by the Hauser-Feshbach statistical model were developed and used to calculate neutron induced nuclear reaction cross sections for targets ranging from osmium (Z = 76) to gold (Z = 79). Of particular interest are the cross sections on Ir and Au including reactions on isomeric targets.
Microwaves improve the rate of many chemical reactions either interacting with the solvent, when the reaction is carried out in solution, or with the surface of a solid substrate where a suitable reagent is dispersed (dry chemistry). A few examples of chemical reactions positively affected by microwaves are described: particularly interesting are those concerning polymers and radio-pharmaceuticals.
During the period covered by this report research has been concerned with the study of photo-induced electron transfer reactions from porphyrins to acceptor molecules with time-resolved Electron Paramagnetic Resonance (EPR) methods. Excited-state electron transfer reactions are of importance from a fundamental point of view and in connection with applications in homogeneous and heterogeneous photosensitization, photopolymerization, and solar energy conversions. For this reason, the study of photo-induced electron transfer reactions is of considerable interest.
In this paper, steady-state isotopic transient kinetic analysis (SSITKA) is used to study two model reactions, CO oxidation and CO-NO reactions, on a typical formulation of a three-way auto-catalyst. Under steady-state conditions, abrupt switches in the isotopic composition of CO ("1"2C"1"6O/"1"3C"1"8O) were carried out to produce isotopic transients in both labeled reactants and products. Along with the determination of the average surface lifetimes and concentrations of reaction intermediates, an analysis of the transient responses along the carbon reaction pathway indicated that the distribution of active sites for the formation of CO_2 was bimodal for both reactions. Furthermore, relatively few surface sites contributed to the overall reaction rate.
The reactions of the hydroxyl radical with hydrocarbons and fluoro hydrocarbons attract significant attention due to their importance in atmospheric chemistry. Its reactions with the two first hydrocarbons, methane and ethane are of special interest because, owing to the small size of these systems, they serve as a prototype for the theoretical studies of hydrogen abstraction reactions. In this work, the reaction and activation energies of the hydroxyl radical abstraction reaction with methane and ethane have been investigated by correlated ab initio and DFT methods. The DFT reaction energies are in good agreement with experimental values, but the activation energies may be in severe error. (authors) 22 refs.
Adenine DNA glycosylase catalyzes the glycolytic removal of adenine from the promutagenic A {center_dot} oxoG base pair in DNA. The general features of DNA recognition by an adenine DNA glycosylase, Bacillus stearothermophilus MutY, have previously been revealed via the X-ray structure of a catalytically inactive mutant protein bound to an A:oxoG-containing DNA duplex. Although the structure revealed the substrate adenine to be, as expected, extruded from the DNA helix and inserted into an extrahelical active site pocket on the enzyme, the substrate adenine engaged in no direct contacts with active site residues. This feature was paradoxical, because other glycosylases have been observed to engage their substrates primarily through direct contacts. The lack of direct contacts in the case of MutY suggested that either MutY uses a distinctive logic for substrate recognition or that the X-ray structure had captured a noncatalytically competent state in lesion ...
Direct nuclear reactions are commonly understood in terms of distorted wave (DW) formalisms. In the case of a single nucleon knockout or transfer reaction the DW analysis provides a reasonable understanding of the observed data. On the other hand the predictions based on different available information inputs have been verified with the observations consistently. In the case of direct reactions involving nuclear clusters however, the DW predictions have been found to disagree with the observations in most cases. The outcome of these and other improvements in the intermediate energy nuclear phenomena involving direct reactions are highlighted. (author). 13 refs., 18 figs.
When clinoptilolite is immobilized in cement-based composites, a series of reactions occur, leading to release of Cs. These reactions occur in three overlapping stages: a rapid ion exchange, followed by a somewhat slower reaction between clinoptilolite and principally the Ca(OH)_2 component of cement, and, in the longer term, slower reactions with C-S-H leading either to formation of low-lime C-S-H at temperatures below 100"0C or 11 A (1.1 nm) tobermorite at higher temperatures. Kinetic data are presented to evaluate the rate of physical consumption of the zeolites at 70 and 150"0C. Reactions occurring above 100"0C appear to result in the development of extensive microcracking of cement-zeolite composites containing 50% zeolite.
The metal parts of cardiac valve prostheses cause reactions in the surrounding tissues of the heart. In some dogs rather abnormal reactions were found, and were attributed to corrosion of the stainless...Full Text Available
This book examines some of the basic principles behind chemical reaction kinetics. Topics considered include the classical trajectory approach to reactive scattering; periodic orbits and theory of reactive scattering; and semiclassical reactive scattering.
The measurement of polarization in backward scattering for the reactions $\\pi^{+} p \\rightarrow p \\pi^{+},K^{+} p \\rightarrow p K^{+}$ and $\\;\\pi^{+} p \\rightarrow \\Sigma^{+} K^{+}$
This report discusses the following topics: Fusion-fission in light nuclear systems; High-resolution Q-value measurement for the {sup 24}Mg+{sup 24}Mg reaction; Heavy-ion reactions and limits to fusion; and Hybrid MWPC-Bragg curve detector development.
The gas-solid reaction and breakthrough curves in the fixed-bed reactor are of great importance, and being influenced by a number of factors makes the prediction of these factors a difficult problem. In this study, the reaction rate between solid sorbents and hydrogen chloride gas at high temperature was first investigated. On the basis of a fixed-bed reactor, the experimental results were analyzed by the shrinking core model of diffusion and surface chemical reaction control. The results showed that reaction rates of two sorbents with hydrogen chloride gas were controlled by the combination of the surface chemical reaction and diffusion of product layers, and the reaction rates nearly keep constant within 15 h of the initial reaction period and then decrease gradually. The results of the breakthrough curves show that solid sorbents in the ...
The A(..pi../sup +/,/sup 3/He)B reaction near threshold is studied in a model where the pion is absorbed by an /sup 4/He constituent of the target nucleus. The predictions of this model using harmonic oscillator cluster wave functions agree semi-quantitatively with the experimental data on the inverse reaction.
Phenothiazine-N-carbonyl chloride inactivated chymotrypsin and trypsin by means of a 1:1 stoicheiometric reaction. Its reaction with chymotrypsin was 29 times as fast as that with...Full Text Available
The measured result of charged multiplicity in cosmic-ray proton induced nuclear reaction from Chinese satellite emulsion is reported. The correlation of shower and heavy particles is discussed and compared with p-emulsion interactions.
Chemical reactions in living cells are under strict enzyme control and conform to a tightly regulated metabolic program. However, uncontrolled and potentially deleterious endogenous reactions occur,...Full Text Available
Heterogeneous gasless reactive systems, including high-energy density metal-nonmetal compositions, have seen increasing study due to their various applications. However, owing to their high reaction temperature, short reaction time, and small scale of heterogeneity, investigation of their reaction mechanisms and kinetics is very difficult. In this study, microstructural changes and the kinetics of product layer growth in the W-Si system was investigated using a high-speed x-ray phase-contrast imaging technique. Using the Advanced Photon Source of Argonne National Laboratory, this method allowed direct imaging of irreversible reactions in the W-Si reactive system at frame rates up to 36 000 frames per second with 4 {mu}s exposure and spatial resolution of 10 {mu}m. Details of the Si melt and reactions between W and Si, that are unable to be viewed with visible-light imaging, were ...
Heterogeneous gasless reactive systems, including high-energy density metal-nonmetal compositions, have seen increasing study due to their various applications. However, owing to their high reaction temperature, short reaction time, and small scale of heterogeneity, investigation of their reaction mechanisms and kinetics is very difficult. In this study, microstructural changes and the kinetics of product layer growth in the W-Si system was investigated using a high-speed x-ray phase-contrast imaging technique. Using the Advanced Photon Source of Argonne National Laboratory, this method allowed direct imaging of irreversible reactions in the W-Si reactive system at frame rates up to 36 000 frames per second with 4 #mu#s exposure and spatial resolution of 10 #mu#m. Details of the Si melt and reactions between W and Si, that are unable to be viewed with visible-light imaging, were ...
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.
ObjectiveTo assess the efficacy and safety of low dose adrenaline injected subcutaneously to prevent acute adverse reactions to polyspecific antivenom serum in patients admitted...Full Text Available
To examine the association of human papillomavirus (HPV) infection with anal squamous cell carcinoma, the authors applied the highly sensitive polymerase chain reaction (PCR) and in situ hybridization...Full Text Available
The high-energy reaction cross sections of Li and Be isotopes are calculated using a simplified Glauber model and densities constrained by the empirical binding energies. We find excellent agreement with experiment, reproducing the large increase for the most neutron-rich nuclei.
IntroductionRadiotherapy outcomes might be further improved by a greater understanding of the individual variations in normal tissue reactions that determine tolerance. Most published...Full Text Available
A sensitive assay based on the polymerase chain reaction for the detection of Ockelbo virus RNA was developed. Two primer pairs from the gene coding for the E2 glycoprotein were chosen. By use of a...Full Text Available
AIMS: To evaluate the sensitivity of the Roche Cobas, Roche Amplicor plate kit, ligase chain reaction (LCR), and an in house polymerase chain reaction (PCR) by titration of purified elementary bodies...Full Text Available
A high-throughput assay for enzyme activity has been developed that is reaction independent. In this assay, a small-molecule yeast three-hybrid system is used to link enzyme catalysis to transcription...Full Text Available
Anaerobic reactions of Rhus vernicifera laccase and its type-2 copper-depleted derivatives with hexacyanoferrate(II) were investigated by absorption and e.s.r. spectroscopy. When native laccase was...Full Text Available
Disclosed are additives for hydrocarbon fuels which are the reaction products of a polyamine and an alkyl ester of acrylic or alkyl acrylic acid. A preferred composition is a mixture of the reaction product and oxygenated or non-oxygenated mono- or polyamines.
One hundred and seventy-nine patients completed a questionnaire focusing on adverse reactions to dental local anesthetics as manifested by 16 signs and symptoms. Twenty-six percent of the participants...Full Text Available
'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.'
The cold fusion reactions leading to superheavy elements with Z=104-116 has been discussed in our model recently [5]. Presently we shortly discuss our model and extend our consideration to fusion reactions ("8"6Kr, "8"7Rb, "8"8Sr)+"2"0"8Pb and "8"6Kr+"2"0"9Bi leading to elements with Z=118-120. The available experimental cross-section data for the reactions are well described.
Efforts has been made to specify surface ozone production in photochemical reaction due to the high concentration of NO_x and photon rays. The secondary reactions has been considered via optical measurements using actinometry and pyranometry which was followed for photochemical reactions at high temperature and because of air pollutants due to the traffic load and because of the inversion in certain days. The concentration of surface ozone which was measured in Tehran city center was in the range of 24- 45 ppb in 1991-1992 and a higher concentration of 45-65 ppb was measured in 1999-2000. This high surface ozone concentration could cause a severe damage to biota, fauna and human health.
A fuel composition comprising a liquid hydrocarbon fuel and a detergent amount of the product of reaction between a polyamine and a stearic acid is described.
A black-disc model combined with accurate matter densities has been used for an investigation of reaction cross sections for {sup 3}He, {sup 4}He and {sup 12}C projectiles. A simple relation is derived between the energy dependence of the reaction cross sections and the strength of the nucleon-nucleon interaction. A comparison is also made of the reaction cross sections for {sup 3}He and {sup 4}He for six different nuclei {sup 12}C, {sup 16}O, {sup 40}Ca, {sup 58,60}Ni and {sup 208}Pb.
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.
Nucleosynthesis and energy production in stellar environments depend critically on nuclear reaction cross sections. Reactions induced by alpha particles are important in the helium burning stage of stars, novae, and supernovae events. They involve light to medium weight nuclei up to about Z=32, and center-of-mass energies up to about 20 MeV. We are working on a project to compile and evaluate cross section data for alpha-induced reactions. These data will eventually be used to derive #alpha#-nucleus potential parameters. (author)
Recent studies indicate that [Fe]-hydrogenases and H{sub 2} metabolism are widely distributed among green algae. The enzymes are simple structured and catalyze H{sub 2} evolution with similar rates than the more complex [Fe]-hydrogenases from bacteria. Different green algal species developed diverse strategies to survive under sulfur deprivation. Chlamydomonas reinhardtii evolves large quantities of hydrogen gas in the absence of sulfur. In a sealed culture of C. reinhardtii, the photosynthetic O{sub 2} evolution rate drops below the rate of respiratory O{sub 2} consumption due to a reversible inhibition of photosystem II, thus leading to an intracellular anaerobiosis. The algal cells survive under these anaerobic conditions by switching their metabolism to a kind of photo-fermentation. Although possessing a functional [Fe]-hydrogenase gene, the cells of Scenedesmus obliquus produce no significant amounts of H{sub 2} under S-depleted conditions. Biochemical ...
Microstructural analyses by advanced metallographic techniques were conducted on mockup welds and a cracked BWR core shroud weld fabricated from Type 304L stainless steel. heat-affected zones of the shroud weld and mockup shielded-metal-arc welds were free of grain-boundary carbide, martensite, delta ferrite, or Cr depletion near grain boundaries. However, as a result of exposure to welding fumes, the heat-affected zones of the welds were significantly contaminated by fluorine and oxygen which migrate to grain boundaries. Significant oxygen contamination promotes fluorine contamination and suppresses classical thermal sensitization, even in Type 304 steels. Results of slow-strain-rate tensile tests indicate that fluorine exacerbates the susceptibility of irradiated steels to intergranular stress corrosion cracking. These observations, combined with previous reports on the strong influence of weld flux, indicate that oxygen and fluorine contamination and ...
Microstructural analyses by several advanced metallographic techniques were conducted on austenitic stainless steel mockup and core shroud welds that had cracked in boiling water reactors. Contrary to previous beliefs, heat-affected zones of the cracked Type 304L, as well as 304 SS core shroud welds and mockup shielded-metal-arc welds, were free of grain-boundary carbides, which shows that core shroud failure cannot be explained by classical intergranular stress corrosion cracking. Neither martensite nor delta-ferrite films were present on the grain boundaries. However, as a result of exposure to welding fumes, the heat-affected zones of the core shroud welds were significantly contaminated by oxygen and fluorine, which migrate to grain boundaries. Significant oxygen contamination seems to promote fluorine contamination and suppress thermal sensitization. Results of slow-strain-rate tensile tests also indicate that fluorine exacerbates the susceptibility of irradiated steels to ...
Aminocyclopropane 1-carboxylic acid (ACC) synthase, a pyridoxal phosphate utilizing enzyme, catalyzes the conversion of S-adenosylmethionine to ACC, the rate limiting step in the biosynthesis of the plant hormone, ethylene. Ethylene, besides being involved in normal plant growth processes, is also produced in response to stress, e.g. wounding, pathogen infection, etc. The authors report the partial purification (400 fold) of ACC synthase from wounded pink tomato pericarp by classical techniques including ammonium sulfate precipitation, ion exchange and phenyl sepharose chromatography. Further purification results in a decrease in specific activity apparently due to the instability of the enzyme and the low levels present in plant tissue. Radiolabeling of a pyridoxal phosphate-utilizing protein in the ACC synthase enriched fraction was achieved. Evidence that this radiolabeled protein is ACC synthase will be presented. Amino acid sequence determination of putative ...
A multifunctional protein kinase, purified from rat liver as ATP-citrate lyase kinase, has been identified as a glycogen synthase kinase. This kinase catalyzed incorporation of up to 1.5 mol of and)2numberSPO4/mol of synthase subunit associated with a decrease in the glycogen synthase activity ratio from 0.85 to a value of 0.15. Approximately 65-70% of the TUPO4 was incorporated into site 3 and 30-35% into site 2 as determined by reverse phase high performance liquid chromatography. This multifunctional kinase was distinguished from glycogen synthase kinase-3 on the basis of nucleotide and protein substrate specificities. Since the phosphate contents in glycogen synthase of sites 3 and 2 are altered in diabetes and by insulin administration, the possible involvement of the multifunctional kinase was explored. Glycogen synthase purified from diabetic rabbits was phosphorylated in vitro by this multifunctional kinase at only 10% of the rate compared to synthase ...
Cell extracts of the thermophile Clostridium thermohydrosulfuricum catalyzed the phosphorylation by (..gamma..-/sup 32/P)ATP of several endogenous proteins with M/sub r/s between 13,000 and 100,000. Serine and tyrosine were the main acceptors. Distinct substrate proteins were found in the soluble (e.g., proteins p66, p63, and p53 of M/sub r/s 66,000, 63,000, and 53,000, respectively) and particulate (p76 and p30) fractions, both of which contained protein kinase and phosphatase activity. The soluble fraction suppressed the phosphorylation of particulate proteins and contained a protein kinase inhibitor. Phosphorylation of p53 was promoted by 10..mu..M fructose 1,6-bisphosphate or glucose 1,6-bisphosphate and suppressed by hexose monophosphates, whereas p30 and p13 were suppressed by 5 ..mu..M brain (but not spinach) calmodulin. Polyamines, including the odd polyamines characteristic of thermophiles, modulated the labeling of most of the phosphoproteins. Apart from ...
Four proteins from NCBI cog1816, previously annotated as adenosine deaminases, have been subjected to structural and functional characterization. Pa0148 (Pseudomonas aeruginosa PAO1), AAur1117 (Arthrobacter aurescens TC1), Sgx9403e, and Sgx9403g have been purified and their substrate profiles determined. Adenosine is not a substrate for any of these enzymes. All of these proteins will deaminate adenine to produce hypoxanthine with k(cat)/K(m) values that exceed 10(5) M(-1) s(-1). These enzymes will also accept 6-chloropurine, 6-methoxypurine, N-6-methyladenine, and 2,6-diaminopurine as alternate substrates. X-ray structures of Pa0148 and AAur1117 have been determined and reveal nearly identical distorted (?/?)(8) barrels with a single zinc ion that is characteristic of members of the amidohydrolase superfamily. Structures of Pa0148 with adenine, 6-chloropurine, and hypoxanthine were also determined, thereby permitting identification of the residues responsible for coordinating the ...
This paper reports on the superiority of zeolites over amorphous solids which is well documented for solid acid catalysts of industrial use. Crystalline supports, likewise, open attractive perspectives for catalysis by metals, alloys, and ligated metal clusters. Size and location of clusters can be controlled by careful design of the preparation conditions. Pore dimensions control the access of reactants to active sites and escape paths for products. Cage dimensions determine which transition states can be attained; window apertures are functional in isolating metal clusters from each other, thus preventing ther coalescence and growth. The ship-in-a-bottle method permits deisgn of fairly large active complexes entrapped in zeolite cages. Orientation of non-spherical molecules in a zeolite proe helps to direct their collision with a metal particle to the head on mode; however, isolated Pt atoms hidden in niches of the pore walls can attack passing molecules at their soft flanks. ...
The aim of present study was to evaluate antioxidant property of Glycyrrhiza glabra root extracts using in vitro models. The dose-dependent aqueous and ethanolic extracts demonstrated the scavenging activity against nitric oxide (concentration that caused 50% inhibition of nitric oxide radicals [IC(50)]=72 and 62.1 microg/ml, respectively), superoxide (IC(50)=64.2 and 38.4 microg/ml, respectively), hydroxyl (IC(50)=81.9 and 63 microg/ml, respectively), DPPH (IC(50)=43.6 and 28.3 microg/ml, respectively) and ABTS(*+) (IC(50)=77.3 and 57.2 microg/ml, respectively) radicals. Further, both extracts showed strong reducing power and iron-chelating capacities. In the Fe(2+)/ascorbate system, both extracts were found to inhibit mitochondrial fraction lipid peroxidation. In copper-catalyzed human serum and low-density lipoprotein oxidation models, both extracts significantly (P<0.05) lengthened the lag phase along with a decline in the oxidation rate, conjugated dienes, ...
During this reporting period four direct coal liquefaction experiments have been completed and a fifth is underway. These experiments have produced conversion and selectivity data on samples of Utah coal slurried in tetralin and catalyzed using iron-titanium hydride. Hydrogen loading of the alloy, catalyst particle size, coal particle size, operating temperatures for alloy addition and liquefaction without the catalysts present, have all been studied during these four experiments. Conversions of 61% DAF in 30 min have been recorded at 485/sup 0/F and 520 psia. The fifth run using the same coal at a reduced particle size has begun, after which we will move to samples of Kentucky and Alabama coals. Equipment manufacture, delivery, and installation delays, totaling over 6 months, greatly reduced the time available for research, making a 6 month no cost extension necessary. The extended time will permit completion of the proposed research tasks. 4 figs., 4 tabs.
An assay for the microsomal hydroxylation of lauric acid (LA), based on HPLC with flow-through radiochemical detection, has been developed. Conditions were optimized for resolution and quantitation of three microsomal metabolites of "1"4C-LA, one of which has not been reported previously as a metabolite of LA in mammalian microsomal incubations. These products, 12-(omega)-hydroxy-LA, 11-(omega-1)-hydroxy-LA, and a novel metabolite, 10-(omega-2)-hydroxy-LA, were isolated by HPLC and identified by gas chromatography/mass spectrometry. In the presence of NADPH, the formation of all three metabolites was linear with time and microsomal protein concentration. Hydrogen peroxide also supported the microsomal metabolism of LA, although the ratio of metabolites was substantially different than that produced by NADPH-supported microsomes. Several biochemical probes (metyrapone, #alpha#-naphthoflavone, 2-diethylaminoethyl-2,2-diphenylvalerate hydrochloride, and 10-undecynoic acid) were used to ...
Acetohydroxyacid synthase (AHAS; EC 2.2.1.6) is the first enzyme in the biosynthetic pathway of the branched-chain amino acids. It catalyzes the conversion of two molecules of pyruvate into 2-acetolactate or one molecule of pyruvate and one molecule of 2-ketobutyrate into 2-aceto-2-hydroxybutyrate. AHAS requires the cofactors thiamine diphosphate (ThDP), Mg{sup 2+} and FAD for activity. The herbicides that target this enzyme are effective in protecting a broad range of crops from weed species. However, resistance in the field is now a serious problem worldwide. To address this, two new sulfonylureas, monosulfuron and monosulfuron ester, have been developed as commercial herbicides in China. These molecules differ from the traditional sulfonylureas in that the heterocyclic ring attached to the nitrogen atom of the sulfonylurea bridge is monosubstituted rather than disubstituted. The structures of these compounds in complex with the catalytic subunit of Arabidopsis ...
Photoinduced charge separation reactions form the basis for energy storage processes in both natural and artificial photosynthesis. Moreover, rapid reversible photoinduced electron transfer reactions are a class of photophysical phenomena that can be exploited to develop schemes for optical switching. Examples from each of these fields are discussed.
A method for the calculation of excitation functions and isomer ratios, for shape isomers, in heavy ion induced reactions is proposed. The calculated values of excitation functions and isomer ratios agree very well with the experimental values for the reaction /sup 238/U(/sup 11/B, alpha 3n)/sup 242/Am. (auth)
This book examines some of the basic principles behind chemical reactions kinetics. Topics considered include ab initio determination of potential energy for chemical reactions; semi-empirical potential energy surfaces; general theory of reactive scattering: different equation approach; and integral equation approach to reactive scattering.
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.
The review is devoted to the use of ionic liquids as solvents, immobilized organocatalysts and reagents in reactions involving carbon acids and 1,3-dipoles, which are widely used to prepare practically valuable organic compounds of various classes. The characteristic features of processes in the presence of ionic liquids, the effects of the structure of cations and anions on the regio-, stereo- and enantioselectivities of reactions and methods of recovery of ionic liquids are considered.
The kinetics of the reaction of carbon dioxide in MDEA solutions were studied both experimentally and theoretically. It is concluded that MDEA acts as a homogeneous catalyst for CO/sub 2/ hydrolysis, and as a result the rate of absorption in aqueous MDEA solutions is significantly larger than one would calculate by simply taking into account the alkalinity of the reaction. A possible zwitterion mechanism is proposed for this reaction. The minor effect of ionic strength were also studied with the presence of other ions. 19 references, 6 figures.
The principle of operation of shaft furnaces is explained and demonstrated in four practical examples. The conditions and parameters determining coke conversion in the combustion zone and in the Boudouard reaction range are described. The combustion process is treated as a whole while the reduction process is discussed separately for the blast furnace, the cupola furnace, and the shaft furnace. The possibilities describing the Boudouard reaction as a function of the temperature level are discussed and consequences are derived for further experimental and theoretical studies.
The reactions of alpha particles on natural abundance chromium have been studied between 40 and 110 MeV, in order to produce "5"2Fe for medical use. The yield of the reaction "5"2Cr(#alpha#,4n)"5"2Fe for Esub(#alpha#) = 85 #-># 53 MeV is only 30 #mu#Ci/#mu#Ah. (orig.).
The catalytic properties of molybdena-alumina catalysts reduced in hydrogen were studied in the function of the reduction temperature, i.e. in the function of the extent of reduction. The deuterium exchange reaction of benzene was used as model catalytic reaction. It was concluded that the reaction rate constant and the multiplicity factor decreased with the extent of reduction parallel with the change in the extent of dehydroxylation of the catalysts. (orig.)
An 'electron-bridge' mechanism of nuclear reaction in an atom or ion by ultra-intense laser fields is presented. A preliminary estimate of the intensity dependence of the rate of disintegration reaction of deuteron nucleus in deuterium atom is made for 800 nm laser fields. For intensities below 5x1021 W/cm2, the rate of disintegration by the 'electron-bridge' mechanism is found to be small, but it rises sharply and becomes large already for ?1022 W/cm2.
R-matrix analyses of neutron-induced reactions for many of the lightest p-shell nuclei are difficult due to a lack of distinct resonance structure in the reaction cross sections. Initial values for the required R-matrix parameters, E,sub(lambda) and ..gamma..sub(lambdac) for states in the compound system, can be obtained from shell model calculations. In the present work, the results of recent shell model calculations for the lithium isotopes have been used in R-matrix analyses of /sup 6/Li+n and /sup 7/Li+n reactions for E sub(n) < 8 MeV. Consequences of the shell model predictions for the level structure of /sup 7/Li and /sup 8/Li on the /sup 6/Li+n and /sup 7/Li+n reaction mechanisms and cross sections are discussed.
This experiment is carried out in the series of the investigation on the damage mechanism of carbon steel. In this paper, the damage situation is considered by structure observations. The test were carried out in 600degC-1200degC temperature range, in blowing an argon gas. The reagents are Na{sub 2}O, Na{sub 2}O{sub 2} and NaOH. From structure observations, the holes are observed on the surface of iron-base material in some test conditions. This result is indicated that the selective reaction occurs. The selective reaction is more obvious as the time exposed to the high temperature is longer. It is considered that the selective reaction occurs after the chemical reaction between iron-base material and sodium compound. The areas, in which Mn-concentration is higher, are observed in products on the surface of specimen. (author)
In the course of designing a catalytic porous membrane reactor for experimental studies, both inside and outside of the non-reaction zones as well as the two ends of the membrane need to be completely sealed to ensure that there is no flow across the membrane in the non-reaction zone. Experiments show that up to 50% of the total flow across the membrane may be contributed by the axial flow along the wall of the non-reaction zones if only one side of the membrane is sealed. Another problem that cannot be solved by sealing is the capillary flow of the catalyst along the tube wall into the non-reaction zones when the catalyst is doped on the membrane. One of the best ways to avoid this axial flow of catalyst would be to use non-porous tubes in the non-reaction zones and join them with the porous membrane tube. In doing so, the cost of the membrane reactor could be reduced simply ...
In terms of the reduced potential energy barrier ? = ?uTS/kT, the rate coefficients for chemical reactions are usually expressed as proportional to e-?. The coupling between vibrational modes of the medium to the reaction coordinate leads to a proportionality of the regularized gamma function of Euler Q(a,?) = ?(a,?)/?(a), with a being the number of modes coupled to the reaction coordinate. In this work, the experimental rate coefficients at various temperatures for several chemical reactions were fitted to the theoretical expression in terms of Q(a,?) to determine the extent of its validity and generality. The new expression affords lower deviations from the experimental points in 29 cases out of 38 and it accounts for the curvature in the logarithmic plots of rate coefficients versus inverse temperature. In the absence of tunneling, conventional theories predict the curvature of these plots to be ...
Nuclear astrophysics seeks for a possible explanation of the observed abundance distribution of various elements and their isotopes in the universe. Most of the relevant nuclear reactions take place in thermally equilibrium environments with bare nuclei, rather than accelerated and head-on colliding situations with low ionisation states of reactant atoms and molecules that are emulated in the laboratories. Moreover, the temperature of the astrophysical environments is quite often low compared to the centre-of-mass energy of the projectile nuclides, that is required for the reaction to be meaningfully investigated in the laboratory. Therefore, an extrapolation of the data on the reaction cross sections to very low energies and to extremely high density situations is generally called for, which are substantially altered every now and then for a number of astrophysically important reactions. The ...
Macrokinetics of benzene sulfonation in liquid-liquid and gas-liquid systems has been studied in continuous mixed reactors. It has been shown that the rate of sulfonation of benzene at 25/sup 0/C in two liquid phases using concentrated sulfuric acid is kinetically controlled. Whereas the rate of the latter reaction by gaseous sulfur trioxide at the same temperature is largely affected by the diffusional phenomena. At this temperature, the rate of reaction in gas-liquid system was described by a model assuming a fast reaction in the liquid phase. However, by increasing the temperature, the fast reaction region gradually changed to instantaneous reaction regime. A model, describing such a regime has also been developed and verified experimentally.
A detailed chemical kinetic reaction mechanism is developed for primary reference fuel mixtures of n-hexadecane and 2,2,4,4,6,8,8-heptamethyl nonane for diesel cetane ratings. The mechanisms are constructed using existing rules for reaction pathways and rate expressions developed previously for the primary reference fuels for gasoline octane ratings, n-heptane and iso-octane. These reaction mechanisms are validated by comparisons between computed and experimental results for shock tube ignition and for oxidation under jet-stirred reactor conditions. The combined kinetic reaction mechanism contains the submechanisms for the primary reference fuels for diesel cetane ratings and submechanisms for the primary reference fuels for gasoline octane ratings, all in one integrated large kinetic reac...
A detailed chemical kinetic reaction mechanism is developed to describe incineration of the chemical warfare nerve agent sarin (GB), based on commonly used principles of bond additivity and hierarchical reaction mechanisms. The mechanism is based on previous kinetic models of organophosphorus compounds such as TMP, DMMP and DIMP that are often used as surrogates to predict incineration of GB. Kinetic models of the three surrogates and GB are then used to predict their consumption in a perfectly stirred reactor fueled by natural gas to simulate incineration of these chemicals. Computed results indicate that DIMP is the only one of these surrogates that adequately describes combustion of GB under comparable conditions. The kinetic pathways responsible for these differences in reactivity are identified and discussed. The most important reaction in GB and DIMP that makes them more reactive than TMP or DMMP is found to be a ...
This paper examines cupric chloride solid conversion during hydrolysis in a thermochemical copper-chlorine (Cu-Cl) cycle for hydrogen production. The hydrolysis reaction is a challenging step, in terms of the excess steam requirement and the decomposition of cupric chloride (CuCl_2) into cuprous chloride (CuCl) and chlorine (Cl_2). The hydrolysis and decomposition reactions are analyzed with respect to the chemical equilibrium constant. The effects of operating parameters are examined, including the temperature, pressure, excess steam and equilibrium conversion. A maximization of yield and selectivity are very important. Rate constants for the simultaneous reaction steps are determined using a uniform reaction model. A shrinking core model is used to determine the rate coefficients and predict the solid conversion time, with diffusional and reaction control. These new results are ...
The kinetics of the reactions between mixed powders of BaCO_3 and CuO, as well as BaCO_3 and Y_2O_3, have been studied using DXRD techniques as a function of particle size, temperature, and CO_2 pressure. Except for initial nucleation phenomena, the reaction rates are governed by shrinking core behavior for BaCO_3 particle sizes between 6 and 33 #mu#m. During the initial stages of the reactions, the surface reaction kinetics are governing, whereas the diffusion of CuO, Y_2O_3, and CO_2 are limiting factors at later stages in the reactions. Quantitative conversion data were used to determine the values of the activation energies and the pertinent diffusivities in these systems.
The reactions between (100) GaAs and the near-noble metals Ni, Pd, and Pt have been investigated by application of high-resolution transmission electron microscopy (TEM), energy-dispersive analysis of x rays in the scanning TEM and Rutherford backscattering spectrometry. Emphasis is placed on the evolution of the phase distributions, film compositions, and interface morphologies during annealing at temperatures up to 480 /sup 0/C. The first phase in the Ni/GaAs reaction is shown to have the nominal composition Ni/sub 3/GaAs. Ternary phases of the type Pd/sub x/GaAs are also found to be the dominant products of the Pd/GaAs reaction. Conversely, only binary phases result from the Pt/GaAs reaction. These observations are used to construct isothermal sections of the M--Ga--As thin-film phase diagrams. The behavior of a thin (1--2 nm) native oxide--hydrocarbon layer during the Ni/GaAs, Pd/GaAs, and Pt/GaAs ...
Theoretical interpretation of fast-charged-particle spectra, observed in the #alpha#-particle-induced reactions on the s-d shell nuclei (A = 24-28), in terms of the Intranuclear Cascade Model and the GDH exciton model (ALICE) is presented. The de-excitation of the excited residual nuclei is accounted for by the evaporation process. The theoretically predicted fast-proton and #alpha#' spectral shapes compare reasonably well with the corresponding measured spectra. However, the magnitude depends critically (as expected) on the reaction cross section employed by the model. As a first step to improve the model predictability of the reaction products, a closer look at the calculation of the #alpha#-particle reaction cross sections was undertaken. A microscopic approach using the optical theorem of Glauber's theory was employed to estimate the #alpha#-induced reaction cross sections for ...
It was previously reported that the tritium tracer method is useful for the quantitative consideration of hydrogen behavior in coal during coal liquefaction reaction. Tetralin is excellent hydrogen donating solvent, and is considered as one of the model compounds of coal. In this study, effects of H2S and H2O on the hydrogen exchange reaction between tetralin and gaseous hydrogen labeled by tritium were investigated. It was suggested that the conversion of tetralin and the hydrogen exchange reaction between gaseous hydrogen and tetralin proceed through the radical reaction mechanism with a tetralyl radical as an intermediate product. When H2S existed in this reaction, the hydrogen exchange yield increased drastically without changing the conversion yield. This suggested that the hydrogen exchange reaction proceeds even in the reaction where ...
The reactions of CF{sub 3}O radicals with (1) NO and (2) NO{sub 2} were studied using two different experimental techniques. A laser photolysis/LIF detection method was applied for measuring the rate constants as a function of temperature (T=222-302 K) and total pressure (p{sub tot}=7-107 mbar). Whereas the reaction with (1) NO was found to be independent of temperature and pressure with k{sub 1}=(4.5{+-}1.2) x 10{sup -11} cm{sup 3}s{sup -1}, the reaction with (2) NO{sub 2} was found to be dependent on both of these variables. The temperature dependence of k{sub 2} in the high pressure limit can be given by the expression k{sub 2{infinity}}{sup -}(T)=(8{+-}5) x 10{sup -13} exp ((863{+-}194) K/T) cm{sup 3}s{sup -1}. The product distributions of the two reactions were determined in separate experiments using steady-state photolysis combined with FTIR spectroscopy. For reaction (1) ...
The absolute cross sections of "2"3Na(p,n)"2"3Mg, "2"7Al(p,n)"2"7Si and "3"0Si(#alpha#,n)"3"3S reactions were measured in the incident energy range of 5.05 to 5.80, 5.80 to 6.25 and 3.975 to 6.235 MeV respectively using a spherically shaped 4#pi# neutron detector. In the energy range 5.80 to 7.80 and 6.235 to 11.30 MeV the absolute cross sections of "2"3Na(p,n)"2"3Mg and "3"0Si-(#alpha#,n)"3"3S reactions were determined by optical model calculations. The cross sections of the inverse reactions "2"3Mg(n,p)"2"3Na and "3"3S(n,#alpha#)"3"0Si were also calculated by the same method for the neutron energy range of 10 keV to 7.50 MeV for each reaction. The cross section of the latter reaction in the neutron energy range of 10 keV to 840 keV was also determined from its inverse reaction "3"0Si(#alpha#,n)"3"3S by the application of the detailed balance theorem. The ...
The effect of adriamycin in combination with radiation on the skin reactions of mouse feet has been examined under a variety of experimental conditions including: (a) hyperthermic treatment of the foot immediately following adriamycin administration, with the former given either just before or just after x irradiation, and (b) fractionated treatments of drug and radiation in a variety of sequences over an 18-day period. In the case of the most severe hyperthermic treatment, no increased radiation reactions were observed in the presence of adriamycin. However, in the case of the less severe hyperthermic treatment a small but significant increase in skin reactions was observed. In the study of fractionated drug and radiation treatments, an enhancement of reaction in those animals receiving combined modality treatment over those receiving radiation alone was seen in those groups where the initiation of ...
In this thesis the rate constants for a number of radical reactions in aqueous solution have been studied in a wide temperature range. The reactions of H with H_2O_2, OH and HO_2 and the reactions of HO_2 with OH, Fe"2"+ and Cu"2"+ have been studied. For each reaction rate constants have been determined as a function of temperature using the technique of high temperature, high pressure (HTP) pulse radiolysis. The rate constants were obtained by fitting a kinetic computer model to the experimental data. From an Arrhenius plot the activation energy of each reaction was determined. The data determined in this way are important for modeling of radiolysis in nuclear light water reactors. A previously developed model for calculation of the effect of water radiolysis products on oxidation and dissolution of spent nuclear fuel has been improved. In the new model, called TraRaMo, ...
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, and thus its influence on the ...
Experimentally investigated nuclear reactions for production of no-carrier-added "7"7Br and "7"7Kr were critically surveyed. The survey covered nine reactions for the formation of "7"7Br and six reactions for "7"7Kr. Both radionuclides are simultaneously produced in many of the studied nuclear processes. The experimental data were compared with the results of nuclear model calculations based on the computer code ALICE-IPPE and the third version of TALYS-based Evaluated Nuclear Data Library, TENDL-2010. Good agreement was found over extended energy regions for the p-, "3He- and #alpha#-particle induced reactions on several target materials. In case of d-induced reactions, however, considerable discrepancies were noted between the experimental and theoretical data. The concordant sets of experimental cross section data for each reaction were fitted by a polynomial ...
The research has involved the characterization of catalyst acidity, [sup 2]D NMR studies of Bronsted acid sites, and kinetic, calorimetric, and spectroscopic studies of methylamine synthesis and related reactions over acid catalysts. Approach of this work was to explore quantitative correlations between factors that control the generation, type, strength, and catalytic properties of acid sites on zeolite catalysts. Microcalorimetry, thermogravimetric analysis, IR spectroscopy, and NMR spectroscopy have provided information about the nature and strength of acid sites in zeolites. This was vital in understanding the catalytic cycles involved in methylamine synthesis and related reactions over zeolite catalysts.
The reactions of native bovine catalase with superoxide and solvated electrons have been investigated using three different methods for generating these reducing substrates: [gamma]-radiolysis of oxygenated or deaerated buffer solutions in the presence of an OH radical scavenger; either xanthine or acetaldehyde with xanthine oxidase; and low-temperature (77 K) [gamma]-radiolysis of buffered ethylene glycol/water solutions with subsequent annealing of samples at 183 K. (Author).
Schemata for modelling combustion processes do not yet include reaction rates for oxygenated fuels like methylal (DMM) which is considered as an additive or replacement for diesel due to its low sooting propensity. Density functional theory (DFT) studies of the possible reaction pathways for different dissociation steps of methylal are presented. Cleavage of a hydrogen bond to the methoxy group or the central carbon atom were simulated at the BLYP/6-311++G{sup **} level of theory. The results are compared to the experiment when dissociating and/or ionising DMM with femtosecond pulses. (author) 1 fig., 1 tab., 1 ref.
Geochemical model is a kind of concept model which describes geochemical processes by means of chemical reaction equations and mathematical formula, and the software based on the concept model are called geochemical modeling code. Geochemical modeling codes can be divided into three categories: mass equilibrium, mass transfer and mass transport code. The major functions of geochemical codes include the calculation of forms of occurrence of elements, the prediction of direction of various geochemical reaction, the dissolution and precipitation of elements, the pH and Eh value, the rate and path of geochemical reaction in aqueous solution.
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.
Nuclear reaction cross-sections for stable strontium and cesium isotopes, which were calculated by different approaches, are compared to available experimental data. Neutron and proton induced reaction cross-sections for the long-lived radionuclides [sup 90]Sr and [sup 137]Cs have been calculated in the energy range from 1 MeV to 10 GeV. Recommendations concerning cross-section calculations for strontium and cesium isotopes at intermediate and high energies are given. (orig.)
Discrepancies between the energy level schemes of "1"0"9Cd determined by radioactive decay studies and "1"1"0Cd(d, t) reaction studies were investigated by a new study of the "1"1"0Cd(d, t) reaction. Sixteen triton groups were found, J/sup pi/ assignments were made, and spectroscopic factors and fullnesses of single particle states were determined and compared with those for isotonic nuclei. The results remove or clarify all previous discrepancies.
The constants, applied in the phenomenological approaches for describing the nuclear reactions with the high transmitted pulse, are obtained within the frames of the multiquark flucton microscopic model. The constants values prove to be universal for all the nuclei and independent on the collision energy and flucton properties (excluding its mass), i.e. the peculiar scaling is manifested in the reaction cross sections. The theoretically obtained values of these constants are in good agreement with the phenomenological values, derived from the (p, p'X) reaction cross sections on the nuclei for X=d, t, "3He
In the reaction sup(nat)Ag + /sup 40/Ar (285 MeV) there have been measured the energy spectra of the isotopes of elements from H to Cl at an emission angle of 40/sup 0/, the energy spectra and angular distributions of /sup 1/H, /sup 2/H, /sup 3/H, and /sup 4/He, and the angular distributions of Li, Be, B, and C. The contribution from multinucleon transfer reactions to the formation of light charged particles is discussed.
Predicted by stochastic models and observed experimentally in a number of isomerization reactions, viscosity-induced solvent effects manifest themselves in a significant departure of the reaction rates from the values expected on the basis of transition state theory. These effects are well understood within the framework of stochastic models; however, the predictive power of such models is limited by the fact that their parameters are not readily available. Experiment and molecular dynamics (MD) simulations can provide such information and can serve as the testing grounds for various stochastic models. In real solvents, a change in viscosity is inevitably associated with variation of at least one of the three factors - temperature, pressure, or solvent identity, resulting in different solv...
The aim of this textbook is to present a relatively simple treatise of the theoretical principles and working methods of photochemistry, key photochemical reactions and important practical applications to enable the reader (a basic knowledge of chemistry is assumed) to work independently is this field. In accordance with the broad scale of this subject, which cuts across numerous disciplines, the topics treated range from photochemical, photophysical and spectroscopical fundamentals, through associated work procedures and methods of evaluation and the various types of reactions to photochemical processes in nature and applied technology. The photochemical properties and reactions of organic and inorganic compounds (preferably coordination compounds) are discussed in each chapter.
A 60-year-old male was bitten by a venomous snake (Vipera ammodytes) and gradually developed signs of an allergic reaction including generalized itching, generalized rash, and chest discomfort. This was followed by severe retrosternal pain with electrocardiographic evidence of an inferior myocardial ischemia progressing to acute myocardial infarction. Cardiac enzymes and troponin, serum tryptase, and histamine were elevated. Coronary arteriography showed normal coronary arteries. This is a characteristic type I variant of Kounis syndrome, which is the concurrence of acute coronary syndromes with conditions associated with mast cell activation including allergic or hypersensitivity reactions as well as anaphylactic or anaphylactoid reactions. This is the first report to show that viper bite...
We have investigated the stability and catalytic activity of epitaxial overlayers of rhodium on Au(111) and Pd(111). Both surfaces show a strong affinity for hydrogen. We have calculated the energy of adsorption both for a strongly and a more weakly adsorbed species; the latter is the intermediate in the hydrogen evolution reaction. Both the energy of activation for hydrogen adsorption (Volmer reaction) and hydrogen recombination (Tafel reaction) are very low, suggesting that these overlayers are excellent catalysts. PMID:21847482
Two patients are described in whom sunburn and electron beam radiodermatitis, respectively, were critical determinants in localizing the initial presentation of drug eruptions. In the first instance, a severe sunburn of the back and thighs was followed 7 months later by the appearance of a toxic epidermal necrolysis drug reaction to trimethoprim-sulfamethoxazole in the exact sites of the previous bullous sunburn reaction. In the second patient, a radiodermatitis of the left upper arm due to electron beam therapy for metastatic breast cancer was followed 7 weeks later by a codeine drug reaction confined to the area of the radiodermatitis. In both instances, oral rechallenge with the offending drug reproduced the eruption.
The energy spectra of few-nucleon transfer reactions obtained by bombarding a /sup 197/Au nucleus with the 341 MeV /sup 20/Ne beam of the Berkeley cyclotron have been analysed successfully in terms of direct surface transfer reactions populating the continuum states. At the grazing angle we are dealing with one-step processes; at forward angle two-step processes have to be taken into account.
In the reactions induced by heavy ions, the study of breakup of heavy ions followed by the fusion of one of the fragments with the target has been of great interest. The present experiments has been performed with a view to compare the measured excitation functions for the same decay channels in "1"2C + "1"6"5Ho and "1"4N + "1"6"3Dy systems
Bremsstrahlung emitted in the {alpha}+p reaction at 50 MeV/nucleon was studied using a 200 MeV {alpha}-particle beam and a liquid hydrogen target. Double-differential photon cross sections were measured over a wide range of angles and energies. Coherent bremsstrahlung was found to be strong for all photon energies. The cross section is enhanced at the highest photon energies and is characteristic of direct capture to the unbound {sup 5}Li ground and first excited state. With direct capture as a limiting case of coherent bremsstrahlung a consistent reaction picture can be obtained.
Monte Carlo criticality calculations have been performed for over 50 years for reactor physics and criticality safety applications. With today's faster computers, these calculations are being carried out to greater precision (smaller uncertainties) in keff, and detailed distributions of power and reaction rates are being computed routinely. This paper provides a review of the fundamental theory of Monte Carlo criticality calculations, with guidance on practical methods for: (1) assuring convergence of both keff and the source distribution, (2) minimizing the bias in keff and reaction rate distributions, and (3) dealing with the under-prediction bias in uncertainties for keff and reaction rate distributions. (authors)
In a double blind test on 40 men and women high performance fencers the influence of a multivitamin-electrolyte-preparation on reaction time, hit-frequency and neuromuscular irritability was determined....Full Text Available
Iodine-125 labelled vinyl and aryl iodides are formed via the reaction of sodium iodide-125 with vinyl- and arylboronic acids. Good yields of isomerically pure products are obtained.
Introduction.Microfluidic technology allows fast reactions in a simple experimental setup, while using very low volumes and amounts of starting material. Consequently, microfluidic technology is an ideal tool for radiolabeling reactions involving short-lived positron emitters. Optimization of the complex array of different reaction conditions requires knowledge of the different reaction parameters linked to the microfluidic system as well as their influence on the radiochemical yields. 1-(5-Deoxy-5-fluoro-?-d-arabinofuranosyl)-2-nitroimidazole ([18F]FAZA) is a frequently used radiotracer for PET imaging of tumor hypoxia. The present study describes the radiosynthesis of [18F]FAZA by means of microfluidic technology and subsequent small animal PET imaging in EMT-6 tumor-bearing mice.Methods...
The nitrogen content of 10 medicinal plant species has been determined by fast-neutron activation analysis (FNAA). Correction factors for the effects of the /sup 16/O(p,..cap alpha..)/sup 13/N knock-on proton-induced reaction and the (n,2n) reactions, which produce interfering positron-emitting radionuclides, have also been determined. The total relative interference from the /sup 16/O(p,..cap alpha..)/sup 13/N and (n,2n) reactions of K, Cl, Fe and Br was found to be 5.1 to 32.1% for the plant samples.
Neopentane, because of its unique structural features, was found to be a useful probe for the assay of the acidity of various zeolites. The C-C bond was attacked by catalyst protons yielding CH/sub 4/ and the isobutyl carbenium ion in equal quantities. The latter either decomposed to produce isobutene or underwent secondary reactions. New avenues for reaction were opened with isobutane. The reaction of the Bronsted protons with the tertiary CH bonds produced H/sub 2/ and the same isobutyl carbenium ion. Hydride ion transfer of the same tertiary hydrogen to existing carbenium ions also occurred and the results showed that about half of the reaction was carried by this pathway. As with Neopentane, the C-C bond could also be attacked yielding the sec-propyl carbenium ion. These tools are being further developed.
We report here results of an application of single-nucleon stripping reactions at high energies (65 MeV/u) in inverse kinematics to obtain spectroscopic factors. From measurements of the partial cross-sections for ground and excited states in residual nuclei formed in one-proton stripping reactions, single particle orbits and occupancies of light nuclei have been studied in the s-d shell. Single proton stripping cross-sections of {sup 25}Al and {sup 26,27,28}P on a Be target have been measured using the S800 spectrograph and the NaI(Tl) array at the NSCL. These results indicate that this technique may provide a general tool for the intermediate energy range analogous to transfer (pick-up) reactions at low-energy.
We report here results of an application of single-nucleon stripping reactions at high energies (65 MeV/u) in inverse kinematics to obtain spectroscopic factors. From measurements of the partial cross-sections for ground and excited states in residual nuclei formed in one-proton stripping reactions, single particle orbits and occupancies of light nuclei have been studied in the s-d shell. Single proton stripping cross-sections of "2"5Al and "2"6","2"7","2"8P on a Be target have been measured using the S800 spectrograph and the NaI(Tl) array at the NSCL. These results indicate that this technique may provide a general tool for the intermediate energy range analogous to transfer (pick-up) reactions at low-energy.
Here we report a new method for measuring the heterogeneous chemistry of submicron organic aerosol particles using a continuous flow stirred tank reactor. This approach is designed to quantify the real time heterogeneous kinetics, using a relative rate method, under conditions of low oxidant concentration and long reaction times that more closely mimic the real atmosphere. A general analytical expression, which couples the aerosol chemistry with the flow dynamics in the chamber is developed and applied to the heterogeneous oxidation of squalane particles by hydroxyl radicals (OH) in the presence of O2. The particle phase reaction is monitored via photoionization aerosol mass spectrometry and yields a reactive uptake coefficient of 0.51+-0.10, using OH concentrations of 1-7x108 molec cdot cm-3 and reaction times of 1.5+-3 hours. This uptake coefficient is larger than that found for the reaction carried ...
The gas-phase reaction of benzene with O(3P) is of considerable interest for modeling of aromatic oxidation, and also because there exist fundamental questions concerning the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties in the product distribution. The reaction proceeds mainly through the addition of the O atom to benzene, forming an initial triplet diradical adduct, which can either dissociate to form the phenoxy radical and H atom, or undergo intersystem crossing onto a singlet surface, followed by a multiplicity of internal isomerizations, leading to several possible reaction products. In this work, we examined the product branching ratios of the reaction between benzene and O(3P) over the temperature range of 300 to 1000 K and pressure range of 1 to 10 Torr. The ...
We show that the recently measured asymmetry in helicity-angle spectra of the #LAMBDA#-hyperons, produced in the reaction pp#->#K"+#LAMBDA#p reaction, and the energy dependence of the total pp#->#K"+#LAMBDA#p cross-section can be explained consistently by the same #LAMBDA#p final-state interaction. Assuming that there is no final-state interaction in the #SIGMA#"0 p channel, as suggested by the available data for the reaction pp#->#K"+#SIGMA#"0p, we can also reproduce the energy dependence of the #LAMBDA#/#SIGMA#"0 production ratio and, in particular, the rather large ratio observed near the reaction thresholds. The nominal ratio of the #LAMBDA# and #SIGMA#"0 production amplitudes squared, i.e. when disregarding the final-state interaction, turns out to be about 3, which is in line with hyperon production data from proton and nuclear targets available at high energies. (orig.)
Several reactions producing odd-Z transactinide compound nuclei were studiedwith the 88-Inch Cyclotron and the Berkeley Gas-Filled Separator at the LawrenceBerkeley National Laboratory. The goal was to produce the same compound nucleus ator near the same excitation energy with similar values of angular momentum via differentnuclear reactions. In doing so, it can be determined if there is a preference in entrancechannel, because under these experimental conditions the survival portion of Swiatecki, Siwek-Wilcznska, and Wilczynski's"Fusion By Diffusion" model is nearly identical forthe two reactions. Additionally, because the same compound nucleus is produced, theexit channel is the same. Four compound nuclei were examined in this study: 258Db, 262Bh, 266Mt, and 272Rg. These nuclei were produced by using very similar heavy-ion induced-fusion reactions which differ only by one ...
Deforestation farther inland causes delayed reactions. When roots no longer hold soil in place, it ends up muddying streams, rivers, and coastal waters. ...
Nuclear reaction rates and opacity are important parameters in stellar evolution. The input physics in a stellar evolution code determines the main theoretical characteristics of the stellar structure, evolution and nucleosynthesis of a star. For different input physics, in this work we calculate stellar evolution models of very massive first stars during the hydrogen and helium burning phases. We have considered 100 and 200M_sun galactic and pregalactic stars with metallicity Z = 10"-"6 and 10"9, respectively. The results show important differences from old to new formulations for the opacity and nuclear reaction rates, in particular the evolutionary tracks are significantly affected, that indicates the importance of using up to date and reliable input physics. The triple alpha reaction activates sooner for pregalactic than for galactic stars.
The available nuclear structure information for all nuclei with mass number A=242 is presented. Various decay and reaction data are evaluated. Adopted data, levels, spin and parity assignments are given.
Detailed level and decay schemes are presented for the nuclei of the A = 101 mass chain. The level properties obtained from decay and reaction experiments are shown in the drawings. Experimental methods, references, and comments are given in the text.
Detailed level and decay schemes are presented for the nuclei of the A = 101 mass chain. The level properties obtained from decay and reaction experiments are shown in the drawings. Experimental methods, references, and comments are given in the text.
The energy level schemes of tin isotopes produced in the heavy ion reactions are presented. The using of #gamma# spectroscopy technique is also described. 4 refs, 12 figs.
Histamine and the histamine receptors are important regulators of a plethora of biological processes, including immediate hypersensitivity reactions and acid secretion in the stomach. In these...Full Text Available
Neutron yield from the "6","7Li + d reaction has been investigated. The results obtained are compared with the published data with some theoretical models.
Neuroleptic malignant syndrome is a life-threatening reaction of neuroleptic medication. The estimated incidence rate of neuroleptic malignant syndrome is between 1% and 1.5% of patients treated with...Full Text Available
Monitoring describes the prospective supervision, observation, and testing of an ongoing process. The result of monitoring provides reassurance that the goal has been or will be achieved, or suggests...Full Text Available
Multi-core MgB_2/Ti/Cu/SS composite wire has been made by the in situ approach. Mechanical properties, interdiffusion reactions and critical currents were studied after heat treatments at temperatures between 500 and 850 "0C. Cu diffusion into the Ti layer occurs for all samples, resulting in the formation of intermetallic compounds at the Cu/Ti interface. EDX analysis has revealed the temperature dependence of all interface reactions. In spite of element reactions the critical current densities 10"5 A cm"-"2 and 10"4 A cm"-"2 were measured in liquid helium at magnetic fields 5 T and 9.5 T, respectively. 10"4 A cm"-"2 at 20 K is measured in an external field of 4 T.
One measured fission and fusion cross sections of "4","6He+"2"0"9Bi and "7Li+"2"0"8Pb reactions within the range from the Coulomb barrier up to 200 MeV. The measured functions of fission and fusion for the mentioned reactions are shown to have close values within the excitation energy wide range. One analyzed the excitation functions of fusion and fission for "4He+"2"0"9Bi, "6He+"2"0"9Bi and "7Li+"2"0"8Pb reactions resulting in formation of "2"1"3","2"1"5At compound systems
Rapid nitridation was used to fabricate reaction-bonded and postsintered -Si6-ZAlZOZN8-Z (Z=1) ceramics with monoclinic ZrO2 added to the starting powder. Thermo-gravimetric analysis revealed that the addition of ZrO2 reduced the starting temperature of the main nitridation reaction. Using a reaction-bonding route with heating rates of 5, 10, and 20C/min, to fabricate -SiAlON ceramics without ZrO2 resulted in unreacted silicon that bled out of the specimens and the Z=1 composition samples did not maintain the original green compact morphology. On the other hand, no such bleeding of melted silicon was observed for samples with ZrO2 additions and the samples following nitridation maintained the original green morphology. The microstructure and mechanical properties of samples produced by rap...
Abstract The characteristics of desulfurization and denitrification with composite absorbent were researched through aqueous absorption experiments. The removal efficiencies of SO2 and NO were up to 100 and 95%, respectively. The composite absorbent included NaClO2 and component M. Existence of component M in the solution could reduce the absorbent cost compared with using sodium chlorite alone. Chlorine dioxide, as main reaction intermediate product, participated in oxidation reaction. The optimal experimental conditions involved NaClO2 concentration of1.13 mmol/L, solution pH of 5.5, molar ratio (M/NaClO2) of 4.1, reaction temperature of 323 K. The optimal solution pH and reaction temperature were both in the required ranges of limestone-gypsum wet flue gas desulfurization (FGD) process....
Purpose - This paper discusses the impact of aesthetic design of smartphones on users' emotional reactions and preferences towards the product. To this end, the paper presents a study that explores emotional reaction of males to varying aesthetic design of the BlackBerry and empirically evaluates their preferences for the BlackBerry in different colours and overlay patterns. The paper then presents the statistical results of the study in an innovative graphical representation. Design/methodology/approach - A quantitative and qualitative research design was used, including three types of data-collection instruments (direct observations, rating scales, and interviews) to investigate if males have a stronger positive emotional reaction for visually treated BlackBerry Pearl devices over the or...
Detailed chemical kinetic reaction mechanisms are developed for combustion of all nine isomers of heptane (C{sub 7}H{sub 16}), and these mechanisms are tested by simulating autoignition of each isomer under rapid compression machine conditions. The reaction mechanisms focus on the manner in which the molecular structure of each isomer determines the rates and product distributions of possible classes of reactions. The reaction pathways emphasize the importance of alkylperoxy radical isomerizations and addition reactions of molecular oxygen to alkyl and hydroperoxyalkyl radicals. A new reaction group has been added to past models, in which hydroperoxyalkyl radicals that originated with abstraction of an H atom from a tertiary site in the parent heptane molecule are assigned new reaction sequences involving additional internal H atom ...
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 ...
The atmospheric processing by ozone of peptide-containing mixed particles was investigated as proxies for biogenic and sea spray primary organic aerosol. Reactions were performed in a flow reactor and particle composition was monitored by photoelectron resonance capture ionization aerosol mass spectrometry. Mixed particles containing dipeptides in a saturated organic matrix of stearic and palmitic acids showed no reaction under ozonolysis at exposure levels of 2.5???10?4?atm s O3. However reactions of mixed particles of a dipeptide (Leu-Leu) in an unsaturated matrix (oleic acid) under the same conditions resulted in a rapid loss of the peptide ion signal, as well as the carrier matrix, and appearance of a number of ion signals corresponding to secondary products. High molecular weight imid...
BackgroundOsseointegration is crucial for the long-term success of dental implants and depends on the tissue reaction at the tissue-implant interface. Mechanical properties and biocompatibility...Full Text Available
Comparisons of calculated neutron yield distributions from #alpha#-particle induced reactions on thick targets are made with measured data to analyze the initial reaction process in the framework of the exciton (hybrid) model code ALICE91 (M. Blann, Lawrence Livermore National Laboratory Report UCID 19614, 1982). We have considered two reaction mechanisms: dissolution of the #alpha# in the nuclear field, and preequilibrium processes initiated by #alpha#-nucleon collisions. Both these processes seem to contribute to the emitted neutron spectra in varying proportions depending on the incident #alpha# energy and possibly on the target nucleus. Contributions from other processes appear to be non-negligible.
Chemically reactive compounds in tissues can be monitored through their products of reaction with biomacromolecules. For the purpose of in vivo dose monitoring, hemoglobin (Hb) has been preferred to...Full Text Available
The reaction of ethanol on unreduced and H{sub 2}-reduced CeO{sub 2} and 1 wt% Pd/CeO{sub 2} has been investigated by steady state reactions, temperature programmed desorption (TPD), and in situ Fourier transform infrared (FT-IR) spectroscopy. Steady state reactions have shown a zero reaction order dependency for diatomic oxygen at and above 20%, while the addition of Pd to CeO{sub 2} decreases the apparent activation energy of the reaction from 75 kJ/mol on CeO{sub 2} alone to 40 kJ/mol (Pd/CeO{sub 2}). TPD experiments following ethanol adsorption on both CeO{sub 2} and Pd/CeO{sub 2} have shown desorption profiles corresponding to unreacted ethanol and various reaction and decomposition products (acetaldehyde, acetone, CO, CO{sub 2}, and methane). Ethanol conversion to reaction products was increased by the addition of Pd, from 15 to 30% on ...
Measurements are made of the isomeric ratio for the (n,2n) and (#betta#,n) reactions on the neutron-deficient nuclei _9_2Mo, _9_0Zr, _8_6Sr and _7_4Se. A method is developed for calculating the isomeric ratio for a low excitation energy of the residual nucleus. The good agreement found between experimental results and calculations for the (#betta#,n) reaction confirms the choices of residual nucleus characteristics, transmission coefficients of neutrons emitted etc. used in the calculations. The results of a study of the (n,2n) reaction were used to find the spin dependences of nuclear level density in the excitation energy region approx. 14 MeV. (author).
A simple semianalytical calculation is used to study how a star reacts when its central stock of hydrogen is exhausted and before the next fusion reaction based on helium begins.
SummaryA microreactor for electrochemical synthesis has been designed and fabricated. It has been shown that different reactions can be carried out successfully using simple protocols.
The core-shell luminol-doped SiO2 nanoparticles were synthesized and immobilized on the surface of chitosan film coating graphite electrode by the self-assembled technique. Then, a novel electrogenerated chemiluminescence (ECL) sensor for pyrogallol was developed based on its ECL enhancing effect for the core-shell luminol-doped silica nanoparticles. The ECL analytical performances and the sensing mechanism of this ECL sensor for pyrogallol were investigated in detail. The corresponding results showed that: compared with the conventional ECL reaction procedures by luminol ECL reaction system, the electrochemical (EC) reaction of pyrogallol and its subsequent chemiluminescence (CL) reaction occurred in the different spatial region whilst offering a high efficiency to couple the EC with the ...
The work is devoted to a microscopic analysis of the reactive capacity of chitin. An algorithm for modeling the deacetylation reaction in a monomeric unit of chitin is described. The reaction coordinate and the potential energy surface topography are determined taking into account the electron-vibrational interaction and low-symmetry perturbations within Jahn-Teller theory. Based on this algorithm, the topological modeling of the deacetylation process is performed for the first time and a mechanism of the biological activity of chitosan is proposed.
The study concerns 1984-1991. The wind park consists of 18 three-bladed 300 kW horizontal axis wind turbines of 35 meters height, and a rotor diameter of 30 meters, seven meteorological towers, and three cluster and control buildings. Aspects studied included disturbance of breeding, resting or feeding, and migrating birds, behavior of birds approaching the wind turbines during the day and night, and bird victims due to collision with the wind turbines and the meteorological towers. The flight behavior of birds approaching the wind park system during daylight is also dealt with. For at least a fifth of the observations it was noted whether the birds passing within 100 meters distance of a turbine showed a reaction or not. The proportion of the reactions was related to the wind park in operation or not in operation, and to the distance between the wind turbines, species, flight height, the passing distance, wind direction and wind force. ...
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 results of photoneutron spectra measurements for the reaction (#gamma#,n) on the Sr-88 nuclei near threshold are presented. The parameters of resonance levels, as well as radiative S_#gamma#"("1") and neutron S_n"("1") strength functions for transitions on the first excited level of Sr-87 were obtained. 2 refs.; 1 fig.; 1 tab.
The status of neutron activation cross sections for some threshold reactions important for reactor materials dosimetry is reviewed. An attempt is made to understand and explain discrepancies between integral and differential data, using recent available experimental results. The importance of standard and benchmark neutron fields for testing differential data for reactor dosimetry is emphasized and the Interlaboratory Reaction Rate (ILRR) program, as well as a similar program pursued by the IAEA, are briefly described.
Lithium (Li) plating-stripping reaction properties at the lithium phosphorus oxynitride glass electrolyte (LiPON)/copper thin film (Cu) interface is improved by the insertion of nano-thickness platinum (Pt) layer at the interface. The LiPON films are formed on mirror-polished lithium-ion conductive solid electrolyte sheets, and current collector thin films of Li, Cu-Pt multi layer, and Cu are formed on the LiPON films. The plating-stripping reactions at the LiPON/current collector films interface are carried out by galvanostatic and potential sweep measurements. Galvanostatic measurements reveal that Pt layer insertion reduces the overvoltage of the reaction and improves its coulomb efficiency. Also, cyclic voltammetry measurement suggests formation of Li-Pt alloys at higher voltages than 0 V (vs. Li/Li{sup +}) during the lithium plating process. Scanning electron microscopy observation clarifies that platinum insertion ...
Calorimetry testing of Tri-n-butyl phosphate (TBP) saturated with strong nitric acid was performed to determine the relationship between vent size and pressure buildup in the event of a runaway reaction. These experiments show that runaway can occur in an open system, but that even when runaway is induced in the TBP/HN0{sub 3} system, dangerous pressure buildup will be prevented with practical vent size.
This report discusses the following topics: Fusion-fission in light nuclear systems; High-resolution Q-value measurement for the {sup 24}Mg+{sup 24}Mg reaction; Heavy-ion reactions and limits to fusion; and Hybrid MWPC-Bragg curve detector development.
Reaction kinetics for the displacement of 5-aminoquinoline (5-Aq) and diethyl sulfide (SEt{sub 2}) from cis-[PtPh{sub 2}(CO)(L)] (L = 5-Aq or SEt{sub 2}) by aliphatic amines was measured for a wide array of amines. Reaction products were characterized by IR and NMR spectroscopies and crystalk structures of selected products were reported. Steric effects on the substitutions were discussed.
An e.p.r. spectrum of the reduced form of the electron-transport component (X), thought to be the primary electron acceptor of Photosystem I, was obtained. By using line-shape simulations of this component...Full Text Available
To simulate the effects of the breakup channel on rearrangement amplitudes, the conventional coupled-reaction-channel (CRC) expansion is augmented by pseudoreaction channels. The construction of the projector for the extended CRC space is discussed, and transition-operator equations on this space are given. By solving the full and post-approximation forms of the CRC equations for a model three-particle problem, the crucial role played by the nonorthogonality terms is demonstrated.
To simulate the effects of the breakup channel on rearrangement amplitudes, the conventional coupled-reaction-channel (CRC) expansion is augmented by pseudoreaction channels. The construction of the projector for the extended CRC space is discussed, and transition-operator equations on this space are given. By solving the full and post-approximation forms of the CRC equations for a model three-particle problem, the crucial role played by the nonorthogonality terms is demonstrated.
An intermetallic compound Sm[sub 2]Fe[sub 17]N[sub x] was synthesized by plasma nitriding of Sm[sub 2]Fe[sub 17] in a stream of N[sub 2]-H[sub 2] mixed gas. The reaction proceeded at a lower temperature (around 423 K) than that of the conventional thermal technique, but not at room temperature. This is discussed on the basis of the difference between the reaction mechanisms of plasma and thermal nitridings. (orig.)
The change of the transport coefficient due to the fusion energy source is studied. The scale invariance property of the reduced set of equations is investigated in the presence of the self-heating term due to the fusion reaction. The pressure gradient as well as the fusion power are the free energy sources that dictate the turbulent transport. It is shown that the burning transport coefficient can have a form with much wider variety, and that the transport property could be different owing to the self-heating by the fusion reactions. (author)
Transient enhanced diffusion in boron-implanted silicon is interpreted as being due to the fact that during rapid thermal annealing a relaxation process takes place, associated with quasi-chemical reactions including defects. A simple analytical model makes it possible to describe the annealing mechanism on a microscopic scale in terms of reaction-diffusion processes. The measured dependences of the boron diffusion coefficient of the enhanced diffusion on time, temperature and implantation energy are satisfactorily explained. (author).
Transient enhanced diffusion in boron-implanted silicon is interpreted as being due to the fact that during rapid thermal annealing a relaxation process takes place, associated with quasi-chemical reactions including defects. A simple analytical model makes it possible to describe the annealing mechanism on a microscopic scale in terms of reaction-diffusion processes. The measured dependences of the boron diffusion coefficient of the enhanced diffusion on time, temperature and implantation energy are satisfactorily explained. (author).
An approach to high energy nuclear reactions (relativistic nuclear physics) is developed on the basis of the quark-parton-flucton concept. The main assumptions underlying the known parton chain model are briefly reformulated, modified and generalized to the flucton case. This new model is used to investigate electron-nuclei and muon-nuclei inclusive reactions within the framework of quantum electrodynamics. The theoretical results are fitted well with existing data. (Auth.).
Projectilelike fragments following the 80 MeV /sup 16/O+/sup 27/Al reaction have been detected using a Bragg-curve spectroscopy ionization chamber (BCS-IC). The atomic number is deduced from the Bragg-peak amplitude. Nitrogen isotopes are clearly resolved using either range or energy loss data. This is the first application of the BCS method for complete ion identification in a heavy-ion-induced reaction.
Projectilelike fragments following the 80 MeV "1"6O+"2"7Al reaction have been detected using a Bragg-curve spectroscopy ionization chamber (BCS-IC). The atomic number is deduced from the Bragg-peak amplitude. Nitrogen isotopes are clearly resolved using either range or energy loss data. This is the first application of the BCS method for complete ion identification in a heavy-ion-induced reaction.
A method and apparatus is provided for detecting explosives by thermal imaging. The explosive material is subjected to a high energy wave which can be either a sound wave or an electromagnetic wave which will initiate a chemical reaction in the explosive material which chemical reaction will produce heat. The heat is then sensed by a thermal imaging device which will provide a signal to a computing device which will alert a user of the apparatus to the possibility of an explosive device being present.
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}. ...
Levels in "7"2Se were observed via in-beam gamma spectroscopy following the "5"8Ni("1"6O,2p) reaction. Spectra and partial energy level schemes are shown. (3 figures) (U.S.).
X-ray diffraction was used to monitor the {ital in} {ital situ} reaction of Pd deposited on Si(111) at room temperature. An ordered silicide forms spontaneously beneath a poorly ordered overlayer. It is commensurate and strained at low coverage, but relaxes to an unstrained state above a critical thickness of 18 A. During both phases of growth sustained intensity oscillations are seen that correspond to a layerwise consumption of the substrate at the buried interface.
The kinetics of the reaction of zirconium phosphates with carbon tetrachloride in sodium and potassium chloride melt as well as the effect of temperature, gas flow, solubility and weight of the solid phase of the phosphate, and stirring of the melt on the chlorination rate has been studied. The kinetic parameters of the reaction (rate constants, activation energy, etc.) have been calculated.
Thermodynamic analysis of dissolution processes of tungsten minerals in citric acid solutions in the absence and in the presence of hydrochloric acid has been carried out by means of calculation of Gibbs energy of the chemical reactions. Kinetic characteristics, such as specific dissolution rates and activation energies, are determined. It is established that the dissolution reactions studied take place in kinetic region. A possibility of scheelite selective dissolution in the presence of other tungsten minerals is shown.
In studying the absorption of carbon dioxide by absorbents impregnated with alkanol amines, researchers used a laboratory-scale packed column to determine the overall gas-phase mass-transfer coefficients and enhancement factors. A model derived for the mechanism of the chemical reaction taking place in the interfacial layer accounts for the effect of the reaction upon the absorption rate better than other models.
Standard SCR catalysts possess high activity for the hydrolysis of HNCO and thus explain the suitability of urea as a selective reducing agent for NO{sub x}. At high space velocities HNCO-slip can get perceptible over the entire temperature range. This can be attributed to the fact that the temperature dependence is strong for the SCR reaction, but weak for the hydrolysis reaction. (author) 3 figs., 5 refs.
The H-D exchange reaction has been measured with the D2-H2O system, for Rhodobacter capsulatus JP91, which lacks the hupSL-encoded hydrogenase, and R. capsulatus BSE16, which lacks the HupUV proteins....Full Text Available
We study the dynamics of scroll vortices in excitable reaction-diffusion systems analytically and numerically. We demonstrate that intrinsic three-dimensional instability of a straight scroll leads to the formation of helicoidal structures. This behavior originates from the competition between the scroll curvature and unstable core dynamics. We show that the obtained instability persists even beyond the meander core instability of the two-dimensional spiral wave. copyright 1998 The American Physical Society.
A facility for studying photon-neutron reactions under a braking #gamma#-beam with an energy of up to 26 MeV from a betratron includes Saratov-2, SM-4A, and IBM AT-386 microcomputers. Neutron detectors, pulsed braking radiation dosimeters, and the devices to control the betatron energy are described.
An experiment to synthesize element 110 by the {sup 59}Co+{sup 209}Bi reaction has bee performed at the SuperHILAC at the Lawrence Berkeley Laboratory. One event with many of the expected characteristics of a successful of {sup 267}110 was observed. This event corresponds to a production cross section of about one picobarn.
The endogenous reverse transcriptase reaction of equine infectious anemia virus (EIAV) has been studied, and conditions allowing synthesis of full-length minus-strand DNA have been determined. In contrast...Full Text Available
The enzyme indol-3-ylacetylglucose synthase (UDP-glucose:indol-3-ylacetate beta-D-glucosyltransferase) catalyses the reaction: [formula: see text] This is the first step in the series of reactions leading...Full Text Available
A ligase chain reaction assay based on a single-base-pair difference in the V9 region of the 16S rRNA gene (16S rDNA) was developed to distinguish between Listeria monocytogenes and other Listeria species....Full Text Available
The cross section for the reaction "8"8Sr(n,p)"8"8Rb was found to be (0.0155 +- 0.0017) mb. This value corresponds well with those calculated by Roy, Hawton, Calamand, and Nasyrov. (author).
A two-step polymerase chain reaction (PCR) procedure with two nested pairs of primers specific for the yadA gene of Yersinia enterocolitica was developed. The PCR assay identified all common pathogenic...Full Text Available
A large IMF- and event characterizing multidetector system (CHICSI) is under development for storage ring experiments. In ''test'' experiments with telescopes of CHICSI type the IMF production has been measured for "1"4N induced reactions at 14A and 32A MeV. Detailed information about the emission sources, particularly from the IMF yield in reactions with isotope separated targets and from isobaric yield ratios in the sub-Coulomb region is discussed. (orig.).
The experimental has been performed with a view to studying complete and incomplete fusion in "1"4N + "1"6"3D_y system below 7 MeV/nucleon. The excitation functions for several reactions have been measured using the activation technique and compared with the theoretical predictions based on statistical models. The codes ALICE-91 and CASCADE used earlier for the analysis of excitation functions in case of "1"2C + "1"6"5H_0 system have been used here also with the same set of input parameters. It has been observed that the theoretical calculations do not match with the experimental excitation functions well but the overall shape of the excitation function is reproduced satisfactorily. The composite nucleus ("1"7"7T_a) formed in this ("1"4N + "1"6"3D_y) case is the same as the one formed in "1"2C + "1"6"5H_0 system studied earlier. Measured excitation functions for the same decay channels in the two cases (i.e. "1"2C + "1"6"5H_0 and "1"4N + "1"6"3D_y) have been ...
We conducted (n, #gamma#) and (d, p) reactions leading to "8"7", "8"8", "8"9"Sr in addition to "8"8Sr (d, t) "8"7Sr and 24 keV neutron capture in "8"8Sr. (orig./HSI).
Chemical looping combustion (CLC) of simulated coal-derived synthesis gas was conducted with NiO oxygen carriers supported on SiO2, ZrO2, TiO2, and sepiolite. The effect of H2S on the performance of these samples for the CLC process was also evaluated. Five-cycle thermogravimetric analysis (TGA) tests at 800 C indicated that all oxygen carriers had a stable performance at 800 C, except NiO/SiO2. Full reduction/oxidation reactions of the oxygen carrier were obtained during the five-cycle test. It was found that support had a significant effect on reaction performance of NiO both in reduction and oxidation rates. The reduction reaction was significantly faster than the oxidation reaction for all oxygen carriers, while the oxidation reaction is fairly slow due to oxygen diffusion on NiO layers. The reaction profile was greatly affected by the presence of H2S, but ...
Results of an experimental study of the interaction of 140 MeV alpha particles with /sup 90/Zr nuclei resulting in fragmentation of the alpha particle are reported. The experimental observations of the study are analyzed and are found to show that alpha particle breakup reactions leading to at least 4-body final states, composed of two charged alpha particle fragments, contribute significantly to the singles yield of charged fragments observed at a fixed forward angle. The conclusions are based on coincidence measurements where one charged fragment is detected at a small forward angle which remains fixed, while the second charged fragment is detected at a series of coplanar secondary angles. The largest coincidence charged particle yield for the multiparticle final state events results from /sup 90/Zr(..cap alpha..,pp)X reactions, where both of the measured protons have energy distributions similar to the proton singles energy distributions. ...
Results of an experimental study of the interaction of 140 MeV alpha particles with _9_0Zr nuclei resulting in fragmentation of the alpha particle are reported. The experimental observations of the study are analyzed and are found to show that alpha particle breakup reactions leading to at least 4-body final states, composed of two charged alpha particle fragments, contribute significantly to the singles yield of charged fragments observed at a fixed forward angle. The conclusions are based on coincidence measurements where one charged fragment is detected at a small forward angle which remains fixed, while the second charged fragment is detected at a series of coplanar secondary angles. The largest coincidence charged particle yield for the multiparticle final state events results from _9_0Zr(#alpha#,pp)X reactions, where both of the measured protons have energy distributions similar to the proton singles energy distributions. The second ...
Cathodic reduction of non-terminal vinylaxides on Hg cathodes in the presence of electrophiles gives reasonable yields of N-acylated enamines in an electrochemically totally irreversible reaction. In the presence of added H-donors rather high selectivity for formation of saturated amides is achieveable. The influence of reaction conditions on product distribution is discussed.
Most chemical reactions in industry and biology are catalytic and play a role at some stage of the processing of about 80% of the goods manufactured in the U.S., yet catalysis is a neglected subject in chemical education. This book integrates the fragmentary treatment accorded the topic until now. It covers, in a unified way, catalysis in solutions, by enzymes, in synthetic polymers within the molecular scale cages of zeolites and other molecular sieves, and on surfaces of inorganic solids. The central ideas are chemical; and principles are illustrated by emphasizing industrial reactions and catalysts.
We consider a nonlinear reaction-diffusion equation settled on the whole euclidean space. We prove the well-posedness of the corresponding Cauchy problem in a general functional setting, namely, when the initial datum is uniformly locally bounded in L^2. Then we adapt the short trajectory method to establish the existence of the global attractor and, if the space dimension is at most 3, we also find an upper bound of its Kolmogorov's entropy.
The catalytic liquefaction of a Chinese bituminous coal was simulated by artificial neural network. Three liquefaction variables, catalyst loading, reaction temperature and reaction time were used as inputs and tetrohydrofuran (THF) conversion and toluene (T) conversion were used as outputs. The artificial neural network, trained by the experimental data, could represent the liquefaction process, with a mean squared deviation of less than 0.025. 7 refs.,1 fig., 3 tabs.
The doping of deuterated polyparaphenylene [C_6D_4]sub(n) with AsF_5 has been investigated by real time neutron diffractometry at 100, 400 and 820 mbar AsF_5 pressure. The reaction appears to be diffusion controlled. Evidence for one doped phase with partial crystalline order was obtained. Structural considerations suggest two polymer chains plus one dopant ''string'' as the repetitive unit. (Auth.).
The reaction of the retinylidene Schiff base in bacteriorhodopsin (bR) to the water-soluble reagent hydroxylamine is enhanced by greater than 2 orders of magnitude under illumination. We have used this reaction as a probe for changes in Schiff base reactivity during the photocycle of wild-type bR and mutants defective in proton transport. We report here that under illumination at pH 6, the D85N mutant has a 20-fold lower rate and the D212N mutant has a greater than 4-fold higher rate for the light-dependent reaction with hydroxylamine compared with wild-type bR. In contrast, the reactivities of wild-type bR and the D96N and T46V mutants are similar. It has been previously shown that the D96N and T46V replacements have no significant effect on the kinetics of M formation but have dramatic effects on rate of the decay of M. We therefore conclude that the hydroxylamine reaction occurs before formation of ...
The experiment on the determination of the tensor polarization of the residual nucleus is described for the reaction "6Li (#alpha#, #alpha#') "6Li. It is based on the unique connection of polarization tensors t_l_m of the residual nucleus for the reaction (#alpha#, #alpha#') and the angular correlation function W (#omega#_1, #omega#_2) for #alpha#'-particle and decay product of this nucleus, where #omega#_1, #omega#_2 are motion directions of #alpha#'-particle and decay product. The angular correlations of #alpha#'-particle and deuteron are measured for the "6Li (#alpha#, #alpha#', d)"4He reaction on the 27.2 MeV #alpha#-particle beam. The recording system consists of six silicon detectors and provides the energy resolution about 0.8 MeV and the angular resolution #+-# 3 deg. The polarization tensors of the residual nucleus "6Li (2.185 MeV, 3"+) are determined as the result of measuring the angular correlations of products ...
Catalytic reactions of 3-methylpentane and 2,3-dimethylbutane on HY, amorphous silica-alumina, and HZSM-5 have been studied at 500{degree}C. Both kinetic phenomena and product selectivities have been reported. Cracking reactions an HZSM-5 can be attributed to initiation through protonation occurring at Bronsted sites. Bimolecular processes leading to chain reaction via hydride transfer are restricted within the narrow pore pentasil zeolite. On HY and amorphous silica-alumina, initiation of cracking also occurs at Bronsted sited. No direct evidence was found for participation of Lewis acid sites on the catalyst framework itself. Following initiation, reactions on these catalysts are accelerated through a chain process occurring at Lewis sites generated by adsorption of product olefins at Bronsted sites. The resulting change in the dominant cracking mechanism is reflected in the product selectivity, ...
Projected scenarios for the proposed Yucca Mountain repository include significant periods of time when high relative humidity atmospheres will be present, thus the reaction processes of interest will include those known to occur under these conditions. The ideal natural analog for the proposed Yucca Mountain repository would consist of natural borosilicate glasses exposed to expected repository conditions for thousands of years; however, the prospects for identifying such an analog are remote, but an important caveat for using natural analog studies is to relate the reaction processes in the analog to those in the system of interest, rather than a strict comparison of the glass compositions. In lieu of this, identifying natural glasses that have reacted via reaction processes expected in the repository is the most attractive option. The goal of this study is to quantify molecular water diffusion in the natural analogs ...
Recent work has indicated that the suppression of boron transient enhanced diffusion (TED) in carbon-rich Si is caused by nonequilibrium Si point defect concentrations, specifically the undersaturation of Si self-interstitials, that result from the coupled out-diffusion of carbon interstitials via the kick-out and Frank--Turnbull reactions. This study of boron TED reduction in Si{sub 1-x-y}Ge{sub x}C{sub y} during 750{sup o}C inert anneals has revealed that the use of an additional reaction that further reduces the Si self-interstitial concentration is necessary to describe accurately the time evolved diffusion behavior of boron. In this article, we present a comprehensive model which includes {l_brace}311{r_brace} defects, boron-interstitial clusters, a carbon kick-out reaction, a carbon Frank--Turnbull reaction, and a carbon interstitial-carbon substitutional (C{sub i}C{sub s}) pairing ...
Recent work has indicated that the suppression of boron transient enhanced diffusion (TED) in carbon-rich Si is caused by nonequilibrium Si point defect concentrations, specifically the undersaturation of Si self-interstitials, that result from the coupled out-diffusion of carbon interstitials via the kick-out and Frank--Turnbull reactions. This study of boron TED reduction in Si_1_-_x_-_yGe_xC_y during 750"oC inert anneals has revealed that the use of an additional reaction that further reduces the Si self-interstitial concentration is necessary to describe accurately the time evolved diffusion behavior of boron. In this article, we present a comprehensive model which includes #left brace#311#right brace# defects, boron-interstitial clusters, a carbon kick-out reaction, a carbon Frank--Turnbull reaction, and a carbon interstitial-carbon substitutional (C_iC_s) pairing reaction that ...
Four very common long term mineralogical changes in salt formations are discussed in the view of the safety considerations for underground repositories. Two of these processes, the 'Hartsalz' and 'Carnallite' dissolution were studied in two scale in situ experiments. The results are presented and compared with the results of the geochemical modelling with the computer code EQ3/6. Furthermore the reactions leading to the formation of the gypsum cap rock on the top of the Zechstein salt formations and to the polyhalitization of anhydrite are discussed. Geological field observations and mineral assemblages agree well with the results of the geochemical modelling employing the Pitzer formalism along with the Harvie, Moller and Weare database. We conclude that once the mechanisms of the chemical reactions are well understood it becomes possible to evaluate realistically whether such processes, when encountered in the repository, are still active or ...
The NiMo sulfide supported on Ketjen Black (KB) was more effective and yielded lighter oil products containing light fractions with their boiling point below 300{degree}C during the two stage liquefaction combining low temperature and high temperature hydrogenation the conventional NiMo/alumina catalyst and FeS2 catalyst. Although the NiMo/alumina yielded increased oil products during the two stage liquefaction, the lighter oil fractions did not increase and the heavier fractions increased mainly. This suggests that the hydrogenation of aromatic rings and successive cleavage of the rings are necessary for producing the light oil, which is derived from the sufficient hydrogenation of aromatic rings using catalysts. For the two stage reaction with NiMo/KB catalyst, it was considered that sufficient hydrogen was directly transferred to coal molecules at the first stage of the low temperature reaction, which promoted the solubilization of coal and ...
In the presence of hydroxyl anion, both formaldehyde and glyoxal are known to undergo rearrangements involving intermolecular and intramolecular hydride transfer (the Cannizzaro and Benzilic acid rearrangements respectively). The authors report ab initio SCF-MO calculations of the transition state geometries, the activation barriers, and the hydrogen isotope effects for these two reactions. The structure of the transition state for the rection involving formaldehyde is usually basis set dependent, becoming more linear and symmetrical as the basis set size increases. In contrast, the analogous transition state for the glyoxal reaction involves a highly non-linear hydride transfer. They find the isotope effects to be quite low for the Cannizzaro reaction, and significantly larger for the non-linear benzilic acid rection, in apparent contradiction to Westheimer's suggestion the isotope effects reach a maximum for linear ...
The formation of ZnTe films was investigated on zinc substrates at 640 K by using the following ion exchange and chemical reaction processes,2Zn{sub (substrate)}+Te{sup 4+}{sub (inmoltensalts)}->2Zn{sup 2+}+Te{sub (onsubstrate)}Zn{sub (substrate)}+Te= {sub (onsubstrate)}-> ZnTe{sub (onsubstrate)}The Te{sup 4+} species was supplied to the substrate via the gas phase, vaporized from the eutectic LiCl-KCl molten salt containing TeCl{sub 4} (0.05-0.9 mol%). The phase of the films obtained depended on the reaction time and the TeCl{sub 4} content in the molten chloride. At low TeCl{sub 4} concentrations, ZnTe alloy was not formed over the entire surface even after 3.6 ks. On the other hand, at high TeCl{sub 4} concentrations, tellurium was detected in addition to the ZnTe compound during the first 0.3 ks of the reaction. By selecting appropriate TeCl{sub 4} concentrations and reaction times, a ...
The technology of minor actinide recycling in fast reactors has been discussed. In CEA, the feasibility study on Am once-through recycling in Phenix core with the moderated target subassemblies (S/As) has been performed. In this report, the evaluation of the heterogeneity effect on the moderated target S/As is described. It was evaluated by the calculation with the continuous energy Monte-Carlo code, MVP, because the accuracy of the deterministic method for the moderated target S/As is unknown. The reaction rates of four isotopes (Am-241, Am-242, Am242m and Am-243) calculated with the heterogeneous model and the homogeneous one were compared. These four isotopes play the important role in Am incineration. It is seen that the homogeneous model overestimates the reaction rates of Am-241 and Am-243 by 4 - 13%, and underestimates those of Am-242 and Am-242m by 13 - 23%. Further investigation made it clear that the overestimation of Am-241 and ...
Apparatus and methods are described for generating heat and electricity from the consumption of a variety of aluminum products. The method consists of (A) a reaction chamber containing an aqueous electrolyte solution and adapted for introduction therein of aluminum pieces of various shapes and sizes up to a certain maximum predetermined size and for effecting a chemical reaction between said aqueous electrolyte and said aluminum pieces yielding aluminum hydroxide and an intermediate reactant; (B) means for feeding said aluminum pieces into said reaction chamber in small quantities upon demand; (C) means for removing the heat generated in said chamber as a result of said reaction; (D) means for removing said aluminum hydroxide reaction product; and (E) means for oxidizing said intermediate reactant in an electrochemical cell, thereby generating electrical energy. The intermediate ...
Apparatus and methods for generating heat and electricity from the consumption of a variety of aluminum products comprise: (A) a reaction chamber containing an aqueous electrolyte solution and adapted for introduction therein of aluminum pieces of various shapes and sizes up to a certain maximum predetermined size and for effecting a chemical reaction between said aqueous electrolyte and said aluminum pieces yielding aluminum hydroxide and an intermediate reactant; (B) means for feeding said aluminum pieces into said reaction chamber in small quantities upon demand; (C) means for removing the heat generated in said chamber as a result of said reaction; (D) means for removing said aluminum hydroxide reaction product; and (E) means for oxidizing said intermediate reactant in an electrochemical cell, thereby generating electrical energy. The intermediate reactant is preferably hydrogen ...
Coal demineralization mechanism and its optimum condition were studied by hydrothermal reaction between Ca(OH)2 and quartz as a coal demineralization model. In experiment, the mixture of powder quartz and Ca(OH)2 water slurry was subjected to reaction in an autoclave under spontaneous pressure at 175-340{degree}C. After dried in N2 gas atmosphere at 105{degree}C, the reaction product was analyzed by X-ray diffraction, thermo-balance and differential thermal analysis. In measurement of quartz conversion, the specimen was analyzed by X-ray diffraction after removal of bound water by heat treatment at 850{degree}C. The mixture of clean coal deashed by NaOH and a fixed amount of quartz was also used as specimen for experiment. As the experimental result, dicalcium silicate hydrate was mainly produced at 175{degree}C, and the product changed into xonotlite through tobermorite by longer treatment at higher temperature. For ...
The pulse radiolysis technique has been employed in studying charge-transfer reactions of anionic C{sub 2}O{sub 4}{sup {minus}}, and cationic C{sub 2}O{sub 4}{sup +} species in supercritical carbon dioxide (scCO{sub 2}) over a range of reduced densities {rho}{sub r} = 0.36--1.5 and at a reduced temperature of T{sub r} = 1.03. The absorption spectrum measured in the visible region with a maximum around 700 nm is assigned to the dimer cation C{sub 2}O{sub 4}{sup +}. The pressure dependence of charge-transfer reactions was examined using dimethylaniline (DMA), benzoquinone (BQ), and oxygen as charge acceptors. The reaction rates of DMA with cations, and BQ with anions are at or near the diffusion-controlled limit. The rates decrease an order of magnitude with increase of pressure. The reaction of C{sub 2}O{sub 4}{sup +} with oxygen is much slower with an almost constant rate over the pressure range ...
The purpose of this study is to prevent the deactivation of catalysts recycled in the 0.1 t/d bench scale unit (BSU). Catalysts recovered during reactions in the BSU and after reactions in the 5-liter autoclave were analyzed, to investigate the influences of the reaction condition on the property and activity of catalysts. Were used {gamma}-iron oxyhydroxide ({gamma}-FeOOH), {alpha}-iron oxyhydroxide ({alpha}-FeOOH), and natural pyrite (FeS2) as catalysts. At the S/Fe atomic ration of 1.2 under the BSU reaction condition, troilite was more easily formed from {gamma}-FeOOH compared with pyrite and {alpha}-FeOOH. As the reaction proceeded through the first, second, and third reactors, the crystal size increased, the pyrrhotite content decreased, and the troilite content increased. Deactivation due to the formation of troilite was irreversible. At the S/Fe of 3.0, however, both the ...
OBJECTIVE:- Tumor necrosis factor (TNF) inhibitors can be used to treat inflammatory bowel disease (IBD) but may lead to anti-nuclear antibody (ANA) positivity and lupus-like reactions. Because of its unique structure, certolizumab has lower rates of these complications. We sought to investigate whether patients who have had lupus-like reactions to infliximab or adalimumab would be able to tolerate certolizumab. METHODS:- We performed a retrospective analysis on the 23 patients at the Roberts Inflammatory Bowel Disease Center who received certolizumab for the treatment of Crohn's disease from March 2008 to June 2009. We identified 6 patients who were switched to this drug because of lupus-like reactions from prior anti-TNF therapy and had documented ANA after the reaction and prior to cert...
The authors developed a method, termed an H-blot, by which the poly(A) tract of any specific mRNA may be detected by RNA filter hybridization after its removal from the body of the mRNA by a RNase H-catalyzed endonucleolytic cleavage in the 3' untranslated region. Using this method, they studied the modulation of the length of the poly(A) tract of rat vasopressin mRNA in vivo during changes in the levels of this mRNA resulting from a physiologic stimulus, osmotic stress. The poly(A) tract of hypothalamic vasopressin mRNA in hydrated rats was, quite remarkably, --250 nucleotides in length, in contrast to that of somatostatin mRNA, which was --30 nucleotides long. Vasopressin mRNA poly(A) tail length increased progressively from --250 to --400 nucleotides with the application of the hyperosmotic stimulus and declined to base line after its removal; somatostatin mRNA poly(A) tail length did not change during osmotic stress. The poly(A) tract length of total ...
Three cDNAs, designated IIA3, IIA3v, and IIA4, coding for P450s in the CYP2A gene subfamily were isolated from a {lambda}gt11 library prepared from human hepatic mRNA. Only three nucleotide differences and a single amino acid difference, Leu{sup 160}{yields}His, were found between IIA3 and IIA3v, indicating that they are probably allelic variants. IIA4 displayed 94% amino acid similarity with IIA3 and IIA3v. The three cDNAs were inserted into vaccinia virus, and recombinant viruses were used to infect human hepatoma Hep G2 cells. Only IIA3 was able to produce an enzyme that had a reduced CO-bound spectrum with a {lambda}{sub max} at 450 nm. This expressed enzyme was able to carry out coumarin 7-hydroxylation and ethoxycoumarin O-deethylation. cDNA-expressed IIA3v and IIA4 failed to incorporate heme and were enzymatically inactive. Analysis of IIA proteins in human liver microsomes, using antibody against rat IIA2, revealed two proteins of 49 and 50 kDa, the former of which appeared to ...
Three cDNAs, designated IIA3, IIA3v, and IIA4, coding for P450s in the CYP2A gene subfamily were isolated from a #lambda#gt11 library prepared from human hepatic mRNA. Only three nucleotide differences and a single amino acid difference, Leu"1"6"0#->#His, were found between IIA3 and IIA3v, indicating that they are probably allelic variants. IIA4 displayed 94% amino acid similarity with IIA3 and IIA3v. The three cDNAs were inserted into vaccinia virus, and recombinant viruses were used to infect human hepatoma Hep G2 cells. Only IIA3 was able to produce an enzyme that had a reduced CO-bound spectrum with a #lambda#_m_a_x at 450 nm. This expressed enzyme was able to carry out coumarin 7-hydroxylation and ethoxycoumarin O-deethylation. cDNA-expressed IIA3v and IIA4 failed to incorporate heme and were enzymatically inactive. Analysis of IIA proteins in human liver microsomes, using antibody against rat IIA2, revealed two proteins of 49 and 50 kDa, the former of which appeared to ...
A WO(3)/TiO(2) composite, hollow-sphere photocatalyst with average diameter of 320 nm and shell thickness of 50 nm was successfully prepared using a template method. UV-vis diffuse reflectance spectra illustrated that the main absorption edges of the WO(3)/TiO(2) hollow spheres were red-shifted compared to the TiO(2) hollow spheres, indicating an extension of light absorption into the visible region of the composite photocatalyst. The WO(3) and TiO(2) phases were confirmed by X-ray diffraction analysis. BET isotherms revealed that the specific surface area and average pore diameter of the hollow spheres were 40.95 m(2)/g and 19 nm, respectively. Photocatalytic experiments indicate that 78% MB was degraded by WO(3)/TiO(2) hollow spheres under visible light within 80 min. Under the same conditions, only 24% MB can be photodegraded by TiO(2). The photocatalytic mineralization of MB, catalyzed by TiO(2) and WO(3)/TiO(2), proceeded at a significantly higher rate under ...
Many hormones elicit effects on target cells by stimulating the enzyme phospholipase-C, which catalyzes the hydrolysis of phosphoinositides to the intracellular second messengers diacylglycerol and inositol phosphates. The present study examined the roles of FSH and guanine nucleotide-binding proteins (G-proteins) in regulating the hydrolysis of phosphoinositides in Sertoli cells. Sertoli cell cultures prepared from 16- to 18-day-old rats were incubated for 24 h with myo-[2-3H] inositol to label endogenous phospholipids. Treatment of cells from 0.5-20 min with preparations of ovine FSH ranging in potency from 1-60 times that of NIH FSH S1 did not affect accumulation of inositol phosphates. Levels of total [3H]inositol phosphates [[3H]inositol mono-, di-, and triphosphates (IP, IP2, and IP3)] in FSH-treated cultures was 75-120% the levels in control cultures over the various time intervals studied. Addition of testosterone and the combination of testosterone plus ...
By catalyzing the rate-limiting step in adipose tissue lipolysis, hormone-sensitive lipase (HSL) is an important regulator of energy homeostasis. The role and importance of HSL in tissues other than adipose are poorly understood. We report here the cloning and expression of a testicular isoform, designated HSL{sub tes}. Due to an addition of amino acids at the NH{sub 2}-termini, rat and human HSL{sub tes} consist of 1068 and 1076 amino acids, respectively, compared to the 768 and 775 amino acids, respectively, of the adipocyte isoform (HSL{sub adi}). A novel exon of 1.2 kb, encoding the human testis-specific amino acids, was isolated and mapped to the HSL gene, 16 kb upstream of the exons encoding HSL{sub adi}. The transcribed mRNA of 3.9 kb was specifically expressed in testis. No significant similarity with other known proteins was found for the testis-specific sequence. The amino acid composition differs from the HSL{sub adi} sequence, with a notable hydrophilic ...
Thromboxane A2, the predominant product of arachidonic acid metabolism in the blood platelet, is a potent vasoconstrictor and platelet agonist. During its biosynthesis from cyclic endoperoxide, 12(S)-hydroxy-5Z,8E,10E-heptadecatrienoic acid (HHT) is formed in equal amounts. The further metabolism of HHT, catalyzed by 15-hydroxyprostaglandin dehydrogenase, leads to 12-oxo-5Z,8E,10E-heptadecatrienoic acid (Oxo-HT). Sample workup procedures are described which allow for the sensitive and reproducible determination of these two arachidonic acid metabolites in human plasma by gas chromatography-mass spectrometry in the presence of deuterated analogues as internal standards. HHT is derivatized to the pentafluorobenzyl ester tert-butyldimethylsilyl ether. In order to enable quantification of low concentrations of about 10 pg/ml in nonstimulated human plasma, the samples have to be purified by HPLC. Oxo-HT is derivatized to the pentafluorobenzyl ester, which is purified by ...
Ultra-low pure Pt-based electrodes (0.04-0.12 mg_P_t/cm"2) were prepared by dual ion-beam assisted deposition (dual IBAD) method on the surface of a non-catalyzed gas diffusion layer (GDL) substrate. Film thicknesses ranged between 250 and 750 A, these are compared with a control, a conventional Pt/C (1.0 mg_P_t_(_M_E_A_)/cm"2, E-TEK). The IBAD electrode constituted a significantly different morphology, where low density Pt deposits (largely amorphous) were formed with varying depths of penetration into the gas diffusion layer, exhibiting a gradual change towards increasing crystalline character (from 250 to 750 A). Mass specific power density of 0.297 g_P_t/kW is reported with 250 A IBAD deposit (0.04 mg_P_t/cm"2 for a total MEA loading of 0.08 mg_P_t/cm"2) at 0.65 V. This is contrasted with the commercial MEA with a loading of 1 mg_P_t_(_M_E_A_)/cm"2 where mass specific power density obtained was 1.18 g_P_t/kW (at 0.65 V), a value typical of current state of the ...
Ultra low loading noble metal (0.04-0.12 mg_P_t/cm"2) based electrodes were obtained by direct metallization of non-catalyzed gas diffusion layers via dual ion beam assisted deposition (IBAD) method. Fuel cell performance results reported earlier indicate significant improvements in terms of mass specific power density of 0.297 g_P_t/kW with 250 A thick IBAD deposit (0.04 mg_P_t/cm"2 for a total MEA loading of 0.08 mg_P_t/cm"2) at 0.65 V in contrast to the state of the art power density of 1.18 g_P_t/kW using 1 mg_P_t_(_M_E_A_)/cm"2 at 0.65 V. In this article we report the peroxide radical initiated attack of the membrane electrode assembly utilizing IBAD electrodes in comparison to commercially available E-TEK (now BASF Fuel Cell GmbH) electrodes and find the pathway of membrane degradation as well. A novel segmented fuel cell is used for this purpose to relate membrane degradation to peroxide generation at the electrode/electrolyte interface by means of ...
Human senescence marker protein 30 (SMP30), which functions enzymatically as a lactonase, hydrolyzes various carbohydrate lactones. The penultimate step in vitamin-C biosynthesis is catalyzed by this enzyme in nonprimate mammals. It has also been implicated as an organophosphate hydrolase, with the ability to hydrolyze diisopropyl phosphofluoridate and other nerve agents. SMP30 was originally identified as an aging marker protein, whose expression decreased androgen independently in aging cells. SMP30 is also referred to as regucalcin and has been suggested to have functions in calcium homeostasis. The crystal structure of the human enzyme has been solved from X-ray diffraction data collected to a resolution of 1.4 {angstrom}. The protein has a 6-bladed {beta}-propeller fold, and it contains a single metal ion. Crystal structures have been solved with the metal site bound with either a Ca{sup 2+} or a Zn{sup 2+} atom. The catalytic role of the metal ion has been ...
We investigate the possibility of kaon condensation in the dense interior of neutron stars through the s-wave interaction of kaons with nucleons. We include nucleon-nucleon interactions by using simple parametrizations of realistic forces, and include electrons and muons in #beta#-equilibrium. The equation of state above the condensate threshold is derived in the mean field approximation. The conditions under which kaon condensed cores undergo a transition to quark matter containing strange quarks are also established.The critical density for kaon condensation lies in the range (2.3-5.0)#rho#_0, where #rho#_0=0.16 fm"-"3 is the equilibrium density of nuclear matter. The critical density depends largely on the value of the strangeness content of the proton, the size of which is controversial. For too large a value of the strangeness content, matter with a kaon condensate is not sufficiently stiff to support the lower limit of 1.44 M_o_e_d_o_t for a neutron star. Kaon condensation ...
The LLNL Chemical & Biological National Security Program (CBNP) provides science, technology and integrated systems for chemical and biological security. Our approach is to develop and field advanced strategies that dramatically improve the nation's capabilities to prevent, prepare for, detect, and respond to terrorist use of chemical or biological weapons. Recent events show the importance of civilian defense against terrorism. The 1995 nerve gas attack in Tokyo's subway served to catalyze and focus the early LLNL program on civilian counter terrorism. In the same year, LLNL began CBNP using Laboratory-Directed R&D investments and a focus on biodetection. The Nunn-Lugar-Domenici Defense Against Weapons of Mass Destruction Act, passed in 1996, initiated a number of U.S. nonproliferation and counter-terrorism programs including the DOE (now NNSA) Chemical and Biological Nonproliferation Program (also known as CBNP). In 2002, the Department ...
The microstructure of Al/{alpha}-Al{sub 2}0{sub 3} composites made by infiltrating Al into dense mullite preforms has been characterized using transmission electron microscopy. Observations revealed that the formation of the Al/Al{sub 2}0{sub 3} composites involves three stages. Initially, Al infiltrates into a dense mullite preform through grain boundary diffusion, and reacts with mullite at grain boundaries to form a partial reaction zone. Then, a complete reaction takes place in the reaction region between the partial reaction zone and the full reaction zone to convert the dense mullite preform to a composite of {alpha}-Al{sub 2}0{sub 3} (matrix) and an Al-Si phase (thin channels). Finally, the reduced Si from the reaction diffuses out of the Al/Al{sub 2}0{sub 3} composite through the metal channels, whereas Al from the molten Al pool is continuously drawn to ...
TiH{sub 2} and TiD{sub 2} thick targets were bombarded with 100 to 200 keV protons or deuterons. Evidence for nuclear reactions was obtained by means of a surface barrier particle detector. Deuteron irradiation of TiD{sub 2} produced these observations: copious {approx}2.5 MeV neutrons and {approx}3 MeV protons from direct D-D reactions; gamma rays from p,{gamma} and n,{gamma} reactions; {approx}14 MeV protons from the secondary d({sup 3}He, p){alpha} reaction; and a signal between {approx}6-12 MeV that Kasagi et al. has tentatively identified as protons from the fusion of three deuterium nuclei. However, this signal has in it a strong interference signal from either neutrons or gamma rays that directly deposit energy in the detector. This interference spectra was measured by placing a thick absorber in front of the detector that stops up to 20 MeV protons, but not gamma rays or neutrons. More ...
To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of ...
This paper describes a reactor design to facilitate a room-temperature nuclear fusion/fission reaction to generate heat without generating unwanted neutrons, gamma rays, tritium, or other radioactive products. The room-temperature fusion/fission reaction involves the sequential triggering of billions of single-molecule, "6LiD 'fusion energy pellets' distributed in lattices of a palladium ion accumulator that also acts as a catalyst to produce the molecules of "6LiD from a solution comprising D_2O, "6LiOD with D_2 gas bubbling through it. The D_2 gas is the source of the negative deuterium ions in the "6LiD molecules. The next step is to trigger a first nuclear fusion/fission reaction of some of the "6LiD molecules, according to the well-known nuclear reaction: "6Li + D #-># 2"4He + 22.4 MeV. The highly energetic alpha particles ("4He nuclei) generated by this nuclear reaction ...
Energy and angular double differential cross-section data of fragments by tens of MeV neutron or proton are important to evaluate dosimetry and radiation effect in devices or instruments, since fragments cause a large local ionization. Up to now, experimental data of the fragment production are very scarce due to experimental difficulties of fragment detection. A bragg curve spectrometer (BCS) for fragment measurement is a gridded-ionization chamber that identify fragments on the basis of the difference of Bragg peak value. The BCS was fabricated to adopt for fragment measurement in neutron-induced reactions and tested with a charged-particle beam and then applied to a neutron field successfully. The structure of BCS is a cylindrical gridded ionization chamber, and filled with a Ar + 10% CH{sub 4} gas at a pressure of 2.7 x 10{sup 4} Pa. To confirm the performance of BCS, the following tests were performed: 1) the saturation property by using {sup 241}Am {alpha} ...
Microstructure of market dynamics is studied through analysis of tick price data. Linear trend is introduced as a tool for such analysis. Trend arbitrage inequality is developed and tested. The inequality sets limiting relationship between trend, bid-ask spread, market reaction and average update frequency of price information. Average time of market reaction is measured from market data. This parameter is interpreted as a constant value of the stock exchange and is attributed to the latency of exchange reaction to actions of traders. This latency and cost of trade are shown to be the main limit of bid-ask spread. Data analysis also suggests some relationships between trend, bid-ask spread and average frequency of price update process.
In pre-experiments a tubular reactor was checked whether it is suitable for kinetic measurement on the system of the silver-catalysed partial oxidation of methanol to formaldehyde. Detrimental effects of heat-transfer and mass-transfer on the experimental results were ruled out. Investigations on the characteristics of the reaction showed that it is possible to manipulate the composition of the product mixture by changing the inlet concentration of the reactants. A modified power-law model was established to describe the reaction kinetics. It considers the preadsorption step of oxygen on the catalysts surface and fits the experimental data quite well. During the rapid oxidation the catalysts surface undergoes a drastic change. It gets coarse and has an adsorption capacity of 11 m{sup 2}/g after being exposed to the reaction mixture. (orig.)
In this paper we describe a fractal assembly of copper nanoparticles on different substrates by controlling the chemical replacement reaction. Through calculation, we found that the 'fractal dimensions' of copper dendrites synthesized by us were about 1.832, which agreed well with the 'fractal dimensions' of natural fern leaves (fractal dimension, 1.826), suggesting that the fern fractal model was useful to describe the self-assembly of our copper nanoparticles during the chemical replacement reaction process. These results will be beneficial for the understanding of the role that highly nonequilibrium conditions play in the formation of fractal clusters as well as the self-assembly mystique of metallic nanoparticles in nonequilibrium conditions and also helpful in the future assembly of complicated nanoarchitectures of metallic nanoparticles for potential applications.
The non-isothermal pyrolysis kinetics of Acetocell (the organosolv) and Lignoboost (kraft) lignins, in an inert atmosphere, have been studied by thermogravimetric analysis. Using isoconversional analysis, it was concluded that the apparent activation energy for all lignins strongly depends on conversion, showing that the pyrolysis of lignins is not a single chemical process. It was identified that the pyrolysis process of Acetocell and Lignoboost lignin takes place over three reaction steps, which was confirmed by appearance of the corresponding isokinetic relationships (IKR). It was found that major pyrolysis stage of both lignins is characterized by stilbene pyrolysis reactions, which were subsequently followed by decomposition reactions of products derived from the stilbene pyrolytic pr...
Favorable reaction channels are searched for in order to obtain the superheavy element "2"9"8114. The interaction energy is supposed to comply with the adiabatic hypothesis. Concerning the deformation energy, a very complete binary macroscopic-microscopic energy method is used to perform calculations. Deformed two-center shell model provides the energy level schemes for shell effects. Yukawa-plus-exponential model gives the macroscopic (liquid drop) part of the total energy. The mass tensor is obtained by the Werner-Wheeler irrotational flow hypothesis. Finally the minimization of the multidimensional action integral produces the highest penetrability values. Kr-projectile reactions provide the best pairs, although generally the presentabilities are very low. (author)
All stable even-A molybdenum isotopes and sup(90,92)Zr have been investigated with the (d, "6Li) reaction at Esub(d) = 45 MeV to study proton- and neutron-pair correlations. Differential cross sections were measured for states up to Esub(x) = 3 MeV in "8"6Sr, sup(88,92,94,96)Zr and up to 6 MeV in "8"8Sr and "9"0Zr. Particular attention was paid to the comparison of #alpha#-pickup data with two-nucleon pickup data. The population of low-lying 0"+ and 5"- states for two-neutron and four-nucleon pickup reactions was calculated using simple phenomenological wave functions for the initial and final states. The results of these calculations are in satisfactory agreement with the data. (orig.).
The condensation reaction of furfural (F) on acetone (Ac) gives a high added value product, the 4-(2-furyl)-3-buten-2-one (FAc), used as aroma in alcohol free drinks, ice, candies, gelatines and other products of current life. This synthesis valorises the residues of sugar cane treatment since furfural is obtained by hydrolysis of sugar cane bagasse followed by vapor training extraction. In the face of numerous and complex reactions involved in this synthesis, it is very complicated to define the kinetic laws from exact stoichiometry. A solution allowing to cope the problem consists in identifying an appropriate stoichiometric model. It does not attempt to represent exactly all the reaction mechanisms, but proposes a mathematical support to integrate available knowledge on the transformati...
The addition of MO{sub x} (M: di- or tri-valent transition metal ion) into cerium dioxide (CeO{sub 2}) enhanced the ability of CeO{sub 2} for the oxygen (O{sub 2})-releasing reaction at lower temperature and swift hydrogen (H{sub 2})-generation reaction. CeO{sub 2}-MO{sub x} (M=Mn, Fe, Ni, Cu) reactive ceramics having high melting points were synthesized with the combustion method from their nitrates for solar H{sub 2} production. The prepared CeO{sub 2}-MO{sub x} samples were solid solutions between CeO{sub 2} and MO{sub x} with the fluorite structure through the X-ray diffractometry measurement. Two-step water-splitting reactions with CeO{sub 2}-MO{sub x} reactive ceramics proceeded at 1573-1773 K for the O{sub 2}-releasing step and at 1273 K for the H{sub 2}-generation step by irradiation of infrared image furnace as a solar simulator. The amounts of O{sub 2} evolved in the O{sub 2}-releasing ...
Although the outer surface of single-walled carbon nanotubes (atomically thin cylinders of carbon) can be involved in a wide range of chemical reactions, it is generally thought that the interior surface of nanotubes is unreactive. In this study, we show that in the presence of catalytically active atoms of rhenium inserted into nanotubes, the nanotube sidewall can be engaged in chemical reactions from the inside. Aberration-corrected high-resolution transmission electron microscopy operated at 80?keV allows visualization of the formation of nanometre-sized hollow protrusions on the nanotube sidewall at the atomic level in real time at ambient temperature. Our direct observations and theoretical modelling demonstrate that the nanoprotrusions are formed in three stages: (i) metal-assisted d...
A general quantum adiabatic theorem with and without the time-dependent orthogonalization is proven, which can be applied to understand the origin of activation energies in chemical reactions. Further proofs are also developed for the oscillating Schwinger Hamiltonian to establish the relationship between the internal (due to time-dependent eigenfunctions) and external (due to time-dependent Hamiltonian) time scales. We prove that this relationship needs to be taken as an independent quantum adiabatic approximation criterion. We give four examples, including logical expositions based on the spin-1/2 two-level system to address the gapped and gapless (due to energy level crossings) systems, as well as to understand how does this theorem allows one to study dynamical systems such as chemical reactions.
Formation of oxidizing and reducing radicals was studied by pulse radiolysis of [Fe(CN)_6]"4"- - BrO_3"- - CN"- system in ethylene glycol - water solvent mixture. Oxidizing #centre dot#BrO_2 and BrO radicals formed by electron scavenging with #centre dot#BrO_2"- were identified and their reactions were investigated. The reaction of hydroxyl radicals with ethylene glycol leads to formation of reactive radicals with reducing properties and of compounds which reduce slowly in dark the ferricyanide formed in the reaction of #centre dot#BrO_2 radical with ferrocyanide. (author) 21 refs.; 7 figs.
This research proposes that the concept of emotional attachment, and specifically the independent constructs of psychological ownership and affective reaction, can help explain many of the endowment effect findings documented in the literature. We define these constructs and then test them across a set of nine studies in which we both replicate previous and generate new endowment effect findings, and then show that psychological ownership and affective reaction can mediate the effects. In doing so, we offer direct empirical support for the idea of emotional attachment as a driver of loss aversion while also providing practitioners and future endowment effect researchers with new insights about the psychological processes that underlie the endowment effect.
The energy spectra and angular distributions of proton emission in a reaction of {sup nat}Fe(n,xp) at a neutron energy of 14.6 MeV are measured by the University of Science and Technology of China multitelescope system. The double-differential cross sections of 16 reaction angles from 25 to 164.5 deg are obtained in this measurement. The statistical errors are reduced largely because of the thick target used. The angular distributions show a slightly energy-dependent forward-backward asymmetry. The angle-integrated proton spectrum is compared with theoretical calculations and other results. The total proton-emission cross section is in fair agreement with the prediction and evaluation.
To measure electron reactions on a picosecond timescale the investigators developed a picosecond pulse-conductivity technique, which makes use of the electron fine-structure pulses of our LINAC (pulse width 25 vs FWHM) to produce excess electrons and now detects changes in sample conductance under optimum conditions with an instrumental response of 18 ps. This resolution is in agreement with a theoretical estimate. This technique has been successfully applied to study excess electron reactions in solvents covering a mobility range from 0.24 to 100 cm/sup 2/V/sup -1/s/sup -1/; extension to lower mobility liquids seem possible.
Photoelectron resonance capture ionization (PERCI) is a soft and sensitive ionization method, based on the attachment of low-energy (<1 eV) photoelectrons to organic analyte molecules. PERCI has been developed in our laboratory for the real-time analysis of organic particles by mass spectrometry, and is employed here to monitor the heterogeneous reaction of ozone with oleic acid. Simplified identification of the reaction products is possible as a result of the soft nature of PERCI, giving predominantly the [M--H](-) ions. The major particle-phase products are identified as: 1-nonanal, nonanoic acid, 9-oxononanoic acid, and azelaic acid, consistent with proposed mechanisms. New insight into this well-studied heterogeneous reaction is gained as additional minor particle-phase products, consistent with the Criegee mechanism, are readily detected. PMID:15468105
TiH{sub 2} and TiD{sub 2} thick targets were bombarded with 100 to 200 keV protons. Evidence for nuclear reactions was obtained by means of a surface barrier particle detector. Proton irradiation of TiD{sub 2} produced the following observations: {alpha} particle emission identified as (p, {alpha}) reactions from {sup 11}B and {sup 7}Li impurities in the target at ppm concentrations; and {approx}3 MeV proton and {approx}1 MeV triton emission from secondary D-D reactions caused by elastic scattering of the primary proton with a target deuteron. A 3.9 MeV {alpha} particle peak measured by others was not observed. (author)
The reduction of oxygen was studied in 0.1 M KCl at 70 deg. C using the rotating disk electrode (RDE) technique on platinum and electrodeposited ZnO thin film electrodes deposited on platinum substrates. In the absence of Zn{sup 2+} ions in solution, a Tafel slope of 139 mV dec{sup -1} was obtained, a value close to that measured on bare platinum electrode (133 mV dec{sup -1}) and ascribed to the limitation of the reaction rate by the first electron transfer. The main difference between the noble metal and the oxide electrode was a shift of the curves towards more negative potentials. In the presence of Zn{sup 2+} ions, the current density decreased significantly and the Tafel slope was measured at 282 mV dec{sup -1} showing that the electrode was partially blocked by zinc oxide formation reaction intermediates.
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 period. When the induction period is completed, oxidation of tetralin follows the mechanism of usual, i.e. initiated, ...
A three-dimensional mathematical thermo-fluid model coupling the electrochemical kinetics with fluid dynamics was developed to simulate the heat and mass transfer in planar anode-supported solid oxide fuel cell (SOFC). The internal reforming reactions and electrochemical reactions of carbon monoxide and hydrogen in the porous anode layer were analyzed. The temperature, species mole fraction, current density, overpotential loss and other performance parameters of the single cell unit were obtained by a commercial CFD code (Fluent) and external sub-routine. Results show that the current density produced by electrochemical reactions of carbon monoxide cannot be ignored, the cathode overpotential loss is the biggest one among the three overpotential losses, and that the proper decrease of the operating voltage leads to the increase of the current density, PEN structure temperature, fuel utilization factor, fuel efficiency and ...
Nuclear battery produces electricity by converting radiation energy into electrical energy. Energy carried by particles emitted by a radioisotope nuclei is much higher than that released in chemical reaction. Reaction with nuclei can potentially produce electricity thousand to million times higher than that of chemical reaction. Unlike NPP that produces large scale alternating current using thermodynamic cycle such as Rankine or Brayton cycles, nuclear battery is designed like other battery or fuel cell, to produce direct current (DC). However, both battery utilize the energy or particles radiating from nuclei of a radioisotope. In this paper, several types of nuclear battery as an energy converter are discussed, including their working mechanisms and examples. Nuclear battery is potential to become a long-life power source for use in wide range of applications, including in medical areas and for instruments in remote areas ...
With the assistance of mechanical activation, yttrium-stabilized #alpha#-SiAlON was prepared by combustion synthesis in air, instead of high-pressure N_2 atmosphere for the first time. The reaction activity of metallic particles was remarkably enhanced by mechanical activation, which conduced the reduction of grain size, increased the total surface area and formation of fresh surface. The formation of #alpha#-SiAlON by combustion synthesis in air was explained by a kinetically induced reaction mechanism, in which both initial formation of #alpha#-SiAlON and following avoidance of oxidation were fulfilled by the retardation of O_2 infiltration owing to the short reaction period and fast cooling rate.
The values of spins, parities, and spectroscopic factors for neutron transfer have been determined for many low-lying states in "9"7Mo and "1"0"1Mo by a study of the (t, d) and (d, p) reactions on the neighbouring even-mass isotopes. Eighteen new values of J"#pi# have been obtained for these nuclei. Values of the fullness and emptiness parameters V"2 and U"2 have been suggested for the 3s_1_/_2 and 2d_5_/_s orbitals in "1"0"0Mo. (Nuclear structure "9"7Mo, "1"0"1Mo, measured J, #pi#, and spectroscopic factors for states up to #approx#2.0 MeV using (d, p) and (t, d) reactions.) (author).
This progress report concerns work completed or initiated since our last report in October of 1980. We have performed experiments in two major areas: photodissociation of organic cations to study the competition between isomerization and fragmentation; and, low energy proton transfer reactions of HCO"+ with selected neutrals. The former area provides a sideline to our combustion studies of proton transfer in hydrocarbon flames, but the question of energy transfer in highly excited gas phase ions impacts directly upon questions closely related to the fate of ions in combustion. The latter area, currently in progress, focuses upon the dynamics of biomolecular reactions of direct relevance to combustion.
Ozone plays a critical role in both the chemistry and radiation balance of the troposphere. Understanding the factors controlling tropospheric ozone levels is critical to our understanding of a variety of issues in global chemistry and climate change. Chlorine atoms have the potential to contribute significantly to the ozone balance in the free troposphere. They can react directly with ozone or alternately, with organics and may actually lead to the formation of ozone in the presence of sufficient NO. Reactions of alkali halides in sea salt particles are a potential source of atomic chlorine, hence reactions of these alkali halides, especially those producing precursors to atomic chlorine, are of great interest. Finally, the mechanisms, intermediates and products of the Cl-biogenic reactions are unknown; these could serve as unique markers of chlorine atom chemistry in the troposphere, and hence are important to define.
The kinetics of the reaction of 2,4-dinitrohalogenobenzenes (chlorine, bromine, and iodine derivatives) with tetraethylammonium azide in acetonitrile and in a mixed acetonitrile-dioxane solvent (80 vol. % dioxane) were studied. It was established that there is a marked increase (by more than three orders of magnitude) in the azidization rate constant in the transition from protic solvents to aprotic media, due to the decrease in the activation energy barrier of the reaction. The nucleophilicity parameters N/sup +/ for the azide ion in the investigated solvents were determined in terms of Ritchie's relationship. It was established that the effect of the nature of the leaving group on the rate constant of the reactions is complex in character, and it was shown that treatment of the relative reactivity series for the investigated substrates must be based on an analysis of the activation parameters and not restricted ...
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).
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.
The pronounced selectivity of near-threshold (p,..pi../sup -/) reactions for high-spin two-particle, one-hole states is exploited, in the first spectroscopic application of a (p,..pi..) reaction, to identify previously unknown 25/2/sup +/ and 21/2/sup +/ (g/sub 9/2/)/sup 3/ states in /sup 89/Zr. Relative cross sections for the two transitions are well reproduced by simple model calculations. The analyzing power for the 25/2/sup +/ state is markedly similar to previous (p/sub pol/,..pi../sup -/) results for two-particle one-hole stretched states in lighter nuclei.
The portion of the potential energy surface (PES) of acetylacetone relevant for the intramolecular proton transfer reaction is studied using ab initio and DFT methods. The best estimate of the barrier governing proton transfer was found to be 3.4 kcal mol{sup -1} at the MP4(FC)/6-311 + G(2d,2p)//MP2(FC)/6-311 + G(2d,2p) level of theory. Six stationary points on the PES were characterized as well as the reaction paths connecting these points. Special attention paid to the pathway of intramolecular proton transfer reveals that the internal rotation of the methyl group adjacent to the carbonyl group and the proton transfer reaction are consecutive processes.
The electrochemical behavior of Sb(III) ions was investigated in LiCl-KCl molten salt at 673K. The reaction mechanism and transport parameters of electroactive species were determined by transient electrochemical techniques (such as cyclic voltammetry, square wave voltammetry, chronopotentiometry and chronoamperometry) at a molybdenum electrode. The results showed that electrochemical reduction of Sb(III) in LiCl-KCl melts occurred in a reaction step with an exchange of three electrons. A voltammogram with a different scan rate in LiCl-KCl containing 1.45x10^-^4molcm^-^3 SbCl3 showed that the deposition/dissolution reaction of Sb(III) ions was not completely reversible. The diffusion coefficient of Sb(III) ions was 1.65(+/-0.01)x10^-^5cm^-^2s^-^1 at 673K. The electroreduction of Sb(III) io...
Abstract This study investigated the effects of Maillard reaction products (MRPs) on in vitro starch hydrolysis, and in vivo blood glucose responses in mice. Four MRPs of various dextrose equivalents were prepared by heating a mixture of hydrolyzed rice starch and glycine at 200C for 4-min. The starch hydrolysis rates of gelatinized rice starch (GRS) decreased as the browning reaction of added MRPs increased. The hydrolysis kinetic constants of the GRS with 5% MRPs were relatively lower than that of GRS without MRPs. Blood glucose responses showed similar tendencies to the in vitro starch hydrolysis results. The activity of digestive enzymes was inhibited by the MRPs. The relative crystallinity of all MRPs (29.9-60.1%) appeared to have higher values than GRS (15.1%). The samples heated to ...
Radiation modification on liquid retention properties of native cassava starch, gelatinized at 85"0C, by graft copolymerization with acrylonitrile was carried out by mutual irradiation to #gamma#-rays. A thin aluminium foil was used to cover the inner wall of the reaction vessel so that the extent of homo polymer could be reduced to be less than 1.6% with a distilled water retention value of 665 g/g of the dry weight of the saponified grafted product. Confirmations of graft copolymerization and saponification reactions were made by the infrared spectrophotometric technique. The combined effect of radiation parameters in terms of an irradiation time and a dose rate to the same total dose on the extent of grafting reaction expressed in terms of grafting parameters which directly influenced liquid retention values was evaluated in conjunction with statistical analysis.
High molecular weight products of the ozonolysis reaction of particle-phase 9-octadecenoic acid (oleic acid) have been studied by photoelectron resonance capture ionization (PERCI) mass spectrometry (MS). Oleic acid particles ( Formula Not Shown , Formula Not Shown ) were reacted with ozone (1.8x10-4atm) in a flow reactor at reaction times of 8 and 23s. Particles were sampled on-line with a differentially pumped particle inlet and chemically analyzed by PERCI-MS. PERCI is a soft ionization method that permits the direct measurement of relatively high molecular weight compounds, facilitating molecular identification. In addition to cyclic oxygenates, such as secondary ozonides and geminal diperoxides that were reported previously, we demonstrate the formation of polymers at the particle sur...
We present a new set of 3.5 Post-Newtonian equations in which Newtonian hydrodynamics is coupled to the nonconservative effects of gravitational radiation emission. Our formalism differs in two significant ways from a similar 3.5 Post-Newtonian approach proposed by Blanchet (1993, 1997). Firstly we concentrate only on the radiation-reaction effects produced by a time-varying mass-current quadrupole $S_{ij}$. Secondly, we adopt a gauge in which the radiation-reaction force densities depend on the fourth time derivative of $S_{ij}$, rather than on the fifth, as in Blanchet's approach. This difference makes our formalism particularly well-suited to numerical implementation and could prove useful in performing fully numerical simulations of the recently discovered $r$-mode instability for rotating neutron stars subject to axial perturbations.
We describe a large class of chemical reaction networks, those endowed with a subtle structural property called concordance. We show that the class of concordant networks coincides precisely with the class of networks which, when taken with any weakly monotonic kinetics, invariably give rise to kinetic systems that are injective --- a quality that, among other things, precludes the possibility of switch-like transitions between distinct positive steady states. We also provide persistence characteristics of concordant networks, instability implications of discordance, and consequences of stronger variants of concordance. Some of our results are in the spirit of recent ones by Banaji and Craciun, but here we do not require that every species suffer a degradation reaction. This is especially important in studying biochemical networks, for which it is rare to have all species degrade.
Using a realistic three-body model, angular distributions for the "1"6O(d,p)"1"7O(1/2"+) reaction, based on the channel coupling array (CCA) theory and various forms of the coupled reaction channel (CRC) method are compared. Despite the different forms and theoretical foundations of these methods, they yield similar angular distributions, within the bound state approximations used herein. The expected breaking of time reversal inveriance in the approximated CCA theory is quite small over most of the angular range. Of all the methods used, coupling effects in the forward directions are largest for the post form of the CRC, indicating that it is the least reliable of the CRC forms for fitting data. (Auth.).
Objectives of the program are to understand the mechanisms of coal liquefaction, to determine the role of catalysts in the direct conversion of coal to liquids, to determine the mechanism of catalyst deactivation and to explore slurry phase catalyst systems. Specific projects include: short-contact time coal liquefaction, mineral matter effects and catalyst studies. During this period, work was performed on: (1) the stability, at reaction temperature, of a recycle solvent obtained from the Lummus Two Stage Liquefaction facility, (2) reactions of preasphaltenes and asphaltenes prepared under various reaction severities, (3) the evaluation of the catalyst level detector installed at the H-Coal facility, (4) the characterization of oil soluble metal compounds with respect to hydrogenation activity, and (5) characterization, deactivation and regeneration of catalysts obtained from both the H-Coal and Lummus facilities.
The combustin of chloroethane is modeled as a stirred reactor so that we can study critical emission characteristics of the reactor as a function of residence time. We examine important operating conditions such as pressure, temperature, and equivalence ratio and their influence on destructive efficiency of chloroethane and production of other chlorinated products. The model uses a detailed chemical kinetic mechanism that we have developed previously for C{sub 3} hydrocarbons. We have added to this mechanism the chemical kinetic mechanism for C{sub 2} chlorinated hydrocarbons developed by Senkan and coworkers. Some reactions have been added to Senkan's mechanism and some of the reaction-rate expressions have been updated to reflect recent developments in the literature. In the modeling calculations, sensitivity coefficients are determined to find which reaction-rate constants have the largest effect on destructive ...
Rye straw was completely hydroliquefied, using red mud or CoO-MoO{sub 3} as the catalyst. Red mud catalyst exhibited a satisfactory activity only in the presence of sulphur at {approx} 673 K. Depending on reaction conditions, different amounts of gaseous and liquid products were formed. Their product distributions were comparable to those obtained in hydroliquefaction of cellulose and lignin. All results could be described by a model which assumed that: pyrolysis precedes hydrogenation of pyrolysis products; CO and CO{sub 2} are products of pyrolysis reaction; and hydrogen is consumed mainly in hydrodeoxygenation reactions. Therefore, from a practical point of view, red mud, which is known as a coal liquefaction catalyst, can also be recommended as a cheap and powerful catalyst in the hydroliquefaction of biomass. 29 refs., 6 figs., 11 tabs.
The CERL Code was developed to describe the solution chemistry of the water on the steam generating side of PWR reactors. It is designed to calculate the equilibrium species distribution resulting from the interaction of impurities, corrosion products, and additives in the aqueous solution. It calculates the extent of ion-ion interactions, the precipitation of insoluble species and the amount of solute that partitions into the vapor phase when some of the water evaporates. This knowledge of the bulk phase equilibrium distribution of species, especially the pH should be useful in describing the corrosion processes at the solid liquid boundary. The code does not calculate any changes in oxidation states or any rates of reaction. Therefore, it is incapable of calculating the actual corrosion rates. It is anticipated that it will be used as a subprogram of a larger program that will include the redox reactions and the rates of the ...
Bio-inspired silver nanoparticles were synthesized with the aid of a novel, non-toxic, eco-friendly biological material namely, banana peel extract (BPE). Boiled, crushed, acetone precipitated, air-dried peel powder was used for reducing silver nitrate. Silver nanoparticles were formed when the reaction conditions were altered with respect to pH, BPE content, concentration of silver nitrate and incubation temperature. The colorless reaction mixtures turned brown and displayed UV-visible spectra characteristic of silver nanoparticles. Scanning electron microscope (SEM) observations revealed the predominance of silver nanosized crystallites after short incubation periods. When the reaction mixtures were incubated for 15 days, some micro-aggregates were also observed. Energy dispersive spectr...
A urine leukocyte count of > or = 50/mm3 together with a bacterial count of > or = 10(5) colony-forming units (CFUs) per milliliter was used to define significant infection in 160 children with neurogenic bladder and evaluate the leukocyte and nitrite components of the Chemstrip 9 test. A Chemstrip 9 leukocyte reading of or = 500 leukocytes together with a positive nitrite reaction occurred in 18 children and had a sensitivity of 40% with a 100% positive predictive value for infection. Other combinations of Chemstrip 9 leukocyte and nitrite reactions were unhelpful or of uncertain value. Selection of up to three specimens from each patient increased the number of samples to 360 and provided general confirmation of the above conclusions. Nitrofurantoin may reduce the sensitivity of the nitrite strip reaction. PMID:8359003
The excitation function of ({alpha},{ital xn}) reactions on {sup 191}Ir (abundance 37.3%) and on {sup 193}Ir (abundance 62.7%) has been measured for the 17--55 MeV alpha-particle bombarding energy range. The stacked foil activation technique and {gamma}-ray spectroscopy were used to determine the cross sections. The experimental data were compared with calculated values obtained by means of a geometry-dependent hybrid model. The initial exciton number {ital n}{sub 0}=4 with {ital n}=2, {ital p}=2, and {ital h}=0 gives the best agreements with the presently measured results. To calculate the excitation function theoretically a computer code was used. This set of excitation functions provides a data basis for probing the validity of combined equilibrium and preequilibrium reaction models in a considerable energy range.
An examination of the kinetics of the alkylation of anisole with 1-hexene and 1-hexanol to produce alkylates over zeolite H-beta is presented. Anisole alkylation is found to occur by a set of parallel reactions when hexene is used as the alkylating agent. When hexyl alcohol is the alkylating agent, the reaction follows a multi-step parallel-series mechanism to form monoalkylates and dihexylether. With 1-hexene, a group of isomeric alkylates, viz., ortho-2-hexyl anisole (2-OHA), ortho-3-hexyl anisole (3-OHA), para-2-hexyl anisole (2-PHA), and para-3-hexyl anisole (3-PHA) was obtained. With hexanol, the olefin (hexene) and dihexyl ether were obtained additionally. The influence of process parameters like temperature, catalyst quantity, and alkylating agent on reaction behavior is reported.
A mass transfer model has been developed to describe the rate of absorption (or desorption) of H{sub 2}S and CO{sub 2} in aqueous blends of a tertiary and a secondary or a primary amine. The model is based on penetration theory, and all significant chemical reactions are incorporated in the model. The reactions are taken to be reversible, with reactions involving only a proton transfer considered to be at equilibrium. The particular amines studied in this research were methyldiethanolamine (MDEA), a tertiary amine, and diethanolamine (DEA), a secondary amine. Key physicochemical data needed in the model, such as diffusion coefficients, kinetic rate constants, and gas solubilities, were measured. Experimental absorption rates of CO{sub 2} and H{sub 2}S were measured in a model gas-liquid contacting device and were compared with model predictions. Experiments were carried out for single amine solutions (both MDEA and DEA) and ...
A large area Bragg curve spectroscopy (BCS) detector and a position sensitive parallel grid avalanche counter have been developed to study heavy ion reactions, such as inelastic excitations and few nucleon transfer reactions near the Coulomb barrier. Reasonably good resolutions have been achieved for energy, atomic number and angle. A theoretical investigation on the mass dependence of the Bragg peak signal from the BCS detector, shows that there is a negligible mass dependence related to the geometry of the detector. The mass number of the heavy ions which cannot be obtained by the above method, has been identified by detecting the corresponding characteristic gamma rays from the product nuclei with two large solid angle gamma ray detectors. (orig.)
A large area Bragg curve spectroscopy (BCS) detector and a position sensitive parallel grid avalanche counter have been developed to study heavy ion reactions, such as inelastic excitations and few nucleon transfer reactions near the Coulomb barrier. Reasonably good resolutions have been achieved for energy, atomic number and angle. A theoretical investigation on the mass dependence of the Bragg peak signal from the BCS detector, shows that there is a negligible mass dependence related to the geometry of the detector. The mass number of the heavy ions which cannot be obtained by the above method, has been identified by detecting the corresponding characteristic gamma rays from the product nuclei with two large solid angle gamma ray detectors. (orig.).
A phenomenon based model for chlorine dioxide delignification of chemical pulp is introduced. The pulp suspension environment is modeled using the concept of two liquid phases, one inside and the other external to the fiber wall. Physico-chemical processes taking place during delignification are implemented with thermodynamic, mass transfer and reaction kinetic models. A broad library of chemical reactions is introduced. Inclusion of each reaction is justified. The model response is tested against experimental laboratory delignification results (o-delignified birch pulp). The experimental data consists of kappa number, hexenuronic acid, inorganic oxy-chlorine compound, and organochlorine (AOX, OX) measurements at several time points during five delignification experiments. The model predic...
Measurements of alpha spectra in the (n, #alpha#) reactions induced on /sup 90,91/Zr at 14.3 and 18.15 MeV incident neutron energy are presented. A microscopic calculation of these spectra has been made using both pick-up and knock-on theories, and in both cases only one overall normalizing factor, which is the same for the two target nuclei and incident energies and all the considered transitions, appears as a free parameter in the calculation. Pick-up calculations provide a very satisfactory reproduction of the data. Knock-on calculations reproduce many qualitative features of the measured spectra, but do not allow a fully satisfactory reproduction of them. While the results obtained do not exclude knock-on contributions to these reactions, their presence is not established.
Differential cross sections of the (#alpha#, t) reactions on "4"5Sc, "5"1V, and "5"9Co nuclei are measured in the 10-71 deg, 10-155 deg, and 10-171 deg angular ranges, respectively, with 27.2 MeV alpha particles. The cross sections have also been calculated on the basis of the distorted wave theory. The possibility of an unambiguous choice of the optical potential for alpha particles is discussed. The angular distribution calculations using several combinations of the optical potentials in the inlet and outlet channels of the reactions show that consistence between the calculations and the measurements is achieved (especially in angular range, less than 90 deg, if one of the potentials is chosen to be a sufficiently deep one.
The /sup 86,88/Sr(d, /sup 3/He)/sup 85,87/Rb reactions were studied at energy of 28 MeV and angular distributions were obtained for all observed states. Spectroseopic factors were extracted from distorted-wave Born-approximation calculations of the cross sections. These spectroacopic factors, and those from the /sup 86,88/Sr(/sup 3/He, d)/sup 87,89/ Y reactions, mixing in the ground state of /sup 88/Sr is inferred. The two g/sub (9/2) neutro n ton orbital populations in /sup 86/Sr. (auth)
In this paper, we prove a uniqueness result in the inverse problem of determining several non-constant coefficients of one-dimensional reaction-diffusion equations. Such reaction-diffusion equations include the classical model of Kolmogorov, Petrovsky and Piskunov as well as more sophisticated models from biology. When the reaction term contains an unknown polynomial part of degree $N,$ with non-constant coefficients $\\mu_k(x),$ our result gives a sufficient condition for the uniqueness of the determination of this polynomial part. This sufficient condition only involves pointwise measurements of the solution $u$ of the reaction-diffusion equation and of its spatial derivative $\\partial u / \\partial x$ at a single point $x_0,$ during a time interval $(0,\\epsilon).$ In addition to this uniqueness result, we give several counter-examples to uniqueness, which emphasize the optimality of our ...
as for direct energy conversion in specialized direct electrical energy conversion plants. Figure 1. An energetic (~163KeV) proton and a 11boron nucleus fuse ...
Thioredoxin, a small, ubiquitous protein which participates in redox reactions through the reversible oxidation of its active center dithiol to a disulfide, is an essential protein in Bacillus...Full Text Available
The Bureau of Mines performed chemical research to elaborate details of sulfur chemistry pertaining to the citrate flue gas desulfurization process in which sulfur dioxide (SO2), absorbed (as bisulfite ion) in a buffered sodium citrate solution, is reduce...
We have synthesized a novel stable precursor, saligenin phosphorotrichloridate, which, on reaction with N-monobiotinyldiamines, generates a series of biotinylated covalent inhibitors of serine esterases....Full Text Available
Cysticercosis is an infection with larval cysts of the cestode Taenia solium. Through pathways that are incompletely understood, dying parasites initiate a granulomatous reaction that,...Full Text Available
Performance on serial tasks is influenced by first- and higher-order sequential effects, respectively due to the immediately previous and earlier trials. As response-to-stimulus interval (RSI)...Full Text Available
Ring opening dynamics of diarylethene derivative (BTF6) in n-hexane are studied by femtosecond transient absorption and time resolved spontaneous fluorescence techniques. Cyclo-reversion time constant is obtained.
Rhizosphere acidification by Fe-deficient bean (Phaseolus vulgaris L.) plants was induced by trace amounts of divalent metal ions (Zn, Mn). The induction of this Fe-efficiency reaction...Full Text Available
We describe a 59-year-old patient who developed acute renal failure because of rhabdomyolysis after extensive red fire ant bites. This case illustrates a serious systemic reaction that may occur from...Full Text Available
When the history of neutrons is considered, three large discoveries are recalled, that is, the discovery of neutrons by Chadwick in 1932, the discovery of the nuclear fission of uranium by Hahn and Strassmann in 1938, and the continuation of chain reaction in nuclear fission by Fermi and others in 1942. In neutron capture reaction, the reaction cross section can become very large. The fields of research, to which neutrons have contributed most as the experimental probe, are neutron activation analysis and neutron diffraction. The development of the prompt gamma ray analyzer at the JRR-3M in Japan Atomic Energy Research Institute is reported. This method eliminates the various defects in ordinary neutron activation analysis. By installing the cold neutron source with hydrogen cooling in the JRR-3M, the new field of research was opened. As the combination of a lead-moderated spectrometer and an electron beam type accelerator, ...
The polymerase chain reaction (PCR) was investigated as a means of diagnosing Mycoplasma pneumoniae infections. The target DNA sequence was a 375-bp segment of the P1 virulence protein. This DNA segment...Full Text Available
Nanoparticles of AgBr were prepared by precipitating AgBr in the water pools of microemulsions consisting of CTAB, n-butanol, isooctane and water. An aqueous solution of AgNO{sub 3} added to the microemulsion was the source of Ag{sup +} ions. The formation of AgBr nanoparticles in microemulsions through direct reaction with the surfactant counterion is a novel approach aimed at decreasing the role of intermicellar nucleation on nanoparticle formation for rapid reactions. The availability of the surfactant counterion in every reverse micelle and the rapidity of the reaction with the counterion trigger nucleation within individual reverse micelles. The effect of the following variables on the particle size and size distribution was investigated: the surfactant and cosurfactant concentrations, moles of AgNO{sub 3} added, and water to surfactant mole ratio, R. High concentration of the surfactant or cosurfactant, or high water ...
The chloromethylation reaction of an asphaltite and styrene graft copolymer followed by the amination of the chloromethylated products was optimized. New strongly basic anion exchangers with an exchange capacity of 2.5 mg-equiv/g and a mechanical strength of 93% were prepared.
We show that the recently measured asymmetry in helicity-angle spectra of the {lambda}-hyperons, produced in the reaction pp{yields}K{sup +}{lambda}p reaction, and the energy dependence of the total pp{yields}K{sup +}{lambda}p cross-section can be explained consistently by the same {lambda}p final-state interaction. Assuming that there is no final-state interaction in the {sigma}{sup 0} p channel, as suggested by the available data for the reaction pp{yields}K{sup +}{sigma}{sup 0}p, we can also reproduce the energy dependence of the {lambda}/{sigma}{sup 0} production ratio and, in particular, the rather large ratio observed near the reaction thresholds. The nominal ratio of the {lambda} and {sigma}{sup 0} production amplitudes squared, i.e. when disregarding the final-state interaction, turns out to be about 3, which is in line with hyperon production data from proton and nuclear targets available at ...
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 ...
Probabilities of flucton production have been calculated for the 1p-shell nuclei and its modification by the Yastrov method. The results obtained are in a qualitative agreement with the data resulting from the analysis of experiment in an assumption of a flucton mechanism of proton-nuclear inclusive reactions with the production of cumulative particles.
Experimental results of nuclear reaction and radiative decay for A = 203 nuclides are evaluated. Adopted properties for all the nine isobars, Au, Hg, Tl, Pb, Bi, Po, At, Rn, Fr of mass 203 are presented. Nothing is yet known for [sup 203]Os. 96 refs.
Experimental results of nuclear reaction and radiative decay for A = 203 nuclides are evaluated. Adopted properties for all the nine isobars, Au, Hg, Tl, Pb, Bi, Po, At, Rn, Fr of mass 203 are presented. Nothing is yet known for "2"0"3Os. 96 refs.
Nucleoside 3'-phosphoramidite and chlorophosphite reagents have been found to react with the lactam function of guanine. This reaction caused unsatisfactory results when oligodeoxyribonucleotides containing...Full Text Available
Pd-Si metallic glasses have been utilized as catalysts in the Fischer-Tropsch reaction. The glasses are selective of ethane, whereas the in-situ crystallized glasses select a range of hydrocarbons characteristic of conventional Pd catalysts. This shift in selectivity has been observed in other hydrogenation reactions. Surface crystallization caused by the reaction conditions causes variable selectivity. Crystallization in reaction conditions has been monitored by DSC. During the course of the grant we developed the use of (+)- apopinene (6,6-dimethyl-1R,5R-bicyclo(3.1.1)hept-2-ene) as a molecular probe for determining the number and kinds of active sites on metallic glass catalysts. To accomplish this we conducted many experiments for comparison on other types of catalysts. These were foils, powders, and highly dispersed metals on several different supports. The glassy surfaces appear to be three ...
A number of agricultural and engineering uses for fixated flue gas desulfurization (FGD) material exist; however, the potential for leaching of hazardous elements has limited widespread application and the processes controlling the leaching of this material are poorly understood. In this study, a flow-through rotating-disk system was applied to elucidate the relative importance of bulk diffusion, pore diffusion, and surface chemical reaction in controlling the leaching of fixated FGD material under pH conditions ranging from 2.2 to 6.8. Changing the hydrodynamics in the rotating disk system did not affect the leaching kinetics at both pH 2.2 and 6.8, indicating that bulk diffusion was not the kinetic-limiting step. Application of the shrinking core model (SCM) to the data suggested a surface reaction-controlled mechanism, rather than a pore diffusion mechanism. The leaching of fixated FGD material increased with decreasing pH, suggesting it can ...
Single crystal tungsten oxide (WO3) nanoparticles were prepared via a microwave-assisted method. Electrochemical activity for hydrogen evolution reaction (HER) on WO3 supported on carbon black (WO3/C) electrocatalyst was first studied in acid solution (0.5 M H2SO4) and alkaline solution (1.0 M KOH) at room temperature. The overall experimental results revealed that the electrocatalytic activity for HER on WO3/C is one order magnitude higher than those obtained with carbon black in 0.5 M H2SO4 and is six times than in the case of carbon black in 1.0 M KOH. These results demonstrated that WO3 could enhance the electrocatalytic activity for hydrogen evolution reaction in acid solution (0.5 M H2SO4) and alkaline solution (1.0 M KOH). On the other hand, the kinetic reaction mechanisms were disc...
Abstract in english Higher olefins are produced as a by product in a number of refinery processes and are one of the potential raw materials to produce propylene. In the present study, FCC model feed compound was considered to explore the olefin cracking features and options to enhance propylene using 30% SAPO-34 zeolite as catalyst in a micro-reactor. The superior selectivity of propylene (73 wt%) and higher total olefin selectivity was obtained over 30% SAPO-34 catalyst than over Y or ZSM- (more) 5 zeolite catalysts. The thermodynamical constraints were found to be relatively less serious in the case of 1-hexene conversion. Most of the 1-hexene follows a direct cracking pathway to give two propylene molecules, due to weak acid sites and better diffusion opportunities. The higher temperature and short residence time could also suppress the hydrogen transfer reactions. From OPE (olefins performance envelop) the products were classified as primary, secondary, or ...
The new proton-induced nuclear reaction data for C, Fe, Cu and Pb for KASKAD-S have been generated using a newly developed data preparation system. The new system utilizes the NJOY and TRANSX codes to prepare these data with the latest evaluation instead of using the SADCO code with the built-in nuclear data. Auxiliary codes have been developed to help the conversion of TRANSX output into the reaction data for running the KASKAD-S. The basic nuclear data selected for this work are the LA150 and KAERI high energy files whose energy ranges are up to 150 and 250 MeV, respectively. The total neutron yields were calculated using KASKAD-S and the new reaction data up to 250 MeV bombarding energy. The calculations were compared with the measurements or MCNPX calculations when the measured data were absent. The comparison shows that our calculations give an overall good agreement with the measurements and MCNPX calculations except ...
The mechanism by which mechanical force regulates the kinetics of a chemical reaction is unknown. Here, we use single-molecule force–clamp spectroscopy and protein engineering to study the effect...Full Text Available
When quantum molecular dynamics (QMD) is applied to the nuclear reactions in theory of relativity region, a number of problems arise, and in order to solve them, the prescription of the extension of ordinary nonrelativistic QMD is introduced, and the analysis of proton incidence reaction by using it is shown. By introducing the interaction corresponding to Lorentz transformation, the problems were solved. QMD is the semiclassical simulation that treats the motion of nucleons represented by Gauss wave packet. The motion of wave packet center is expressed by Newton equations and two-nucleon collision. The introduction of the interaction corresponding to Lorentz transformation is explained. As the result of the introduction, through the relative distance of two particles, the interaction becomes to depend on momentum. The phase distribution function of one body corresponding to Lorentz transformation is used for calculating the final state Pauli ...
Patients experiencing several cancers can be a challenge, as optimal treatment options for the different cancers might interfere with each other. In this case report, we present a woman diagnosed with...Full Text Available
Lumbricus terrestris (Annelid, Oligocheta) is capable of cellular- and humoral-specific reactions against natural antigens. Is this earthworm able to elaborate a response of antibody type against a...Full Text Available
The notes describe in detail primary and secondary galvanic cells, fuel cells, electrochemical synthesis and electroplating processes, corrosion: measurments, inhibitors, cathodic and anodic protection, details of metal dissolution reactions, Pourbaix diagrams and purification of waste water from galvanic industries.
BackgroundAllergic Contact Dermatitis (ACD) is regarded as a T-cell-mediated delayed-type hypersensitivity reaction. We studied the kinetics of the expression of CS-1 fibronectin,...Full Text Available
On the basis of the phenomenological model for baryon resonance production in lepton nucleon and lepton nucleus scattering we investigate to what extent quark hadron duality is applicable to the neutrino structure functions and how it compares with duality in electron scattering.
The development of detailed chemical kinetic reaction mechanisms for oxidation of n-octane and iso-octane is described, with emphasis on the factors which are specific to many large hydrocarbon fuel molecules. Elements which are of particular importance are found to include site-specific abstraction of H atoms, radical isomerization of alkyl radicals by internal H atom abstraction, and rapid ..beta..-scission of the alkyl radicals. These features, combined with distinctions in the types of intermediate olefin species produced, are used to explain the significant differences in the rate of oxidation between n-octane and iso-octane. Experimental results from the turbulent flow reactor and low pressure laminar flames, using both n-octane and iso-octane as fuels, are used to test the reaction mechanisms and indicate those parts of the total mechanisms which are in greatest need of further development and refinement. It is found that the ...
The cross sections of "2"0"4Pb(n,2n)"2"0"3Pb and "2"0"6Pb(n, #alpha#)"2"0"3Hg reactions have been measured by using the activation method in the neutron energy range of 13.50-14.81 MeV. Neutron fluence dose was calibrated with the cross sections of "2"7Al(n, #alpha#)"2"4Na reaction and neutron energies were determined by using the cross section ratios of "9"0Zr(n,2n)"8"9"m"+"gZr to "9"3Nb(n,2n)"9"2"mNb reactions. The results obtained are compared with the published data.
Charge reduction electrospray mass spectrometry (CREMS) reduces the charge states of electrospray-generated ions, which concentrates the ions from a protein into fewer peaks spread over a larger...Full Text Available
To attain reproducible and stable contacts to compound semiconductor devices, it is necessary to achieve thermodynamically stable phases after the reaction of metals with the compound semiconductor. In this study, the final phases produced by the reactions between GaAs and thin metal films of Co, Rh, Ir, Ni, Pd, and Pt have been investigated. They are identified as MGa for M = Co, Rh, Ni, Pd, and Pt, monoarsenides of Co and Ni, diarsenides of Rh, Ir, Pd, and Pt, and Ir/sub 3/Ga/sub 5/. These phases, if deposited directly onto GaAs, will produce thermally stable contacts. In addition to the identification of these stable phases, analyses of the products of thin-film M/GaAs reactions by transmission electron microscopy, x-ray diffraction, and Rutherford backscattering spectrometry reveal the distribution, grain size, and crystallographic texture of these end phases. Trends in these observations across the six metal/GaAs ...
Chronic autoimmune or pathogen-induced immune reactions resulting in lymphoid neogenesis are associated with development of malignant lymphomas, mostly extranodal marginal zone B-cell lymphomas (MZBCLs)....Full Text Available
Having recently discovered that polynuclear heteroaromatic nitrogen compounds can be selectively reduced only at the nitrogen containing ring, we have now turned our attention towards the cleavage of the carbon nitrogen bonds in this reduced ring. Highlights for this reporting period are: (1) Studies with the 50% nickel oxide catalyst clearly show that 1,2,3,4-tetrahydroquinoline(THQ) provides approximately 20% more liquid product that does quinoline. Thus a first step selective hydrogenation to 1,2,3,4-THQ would enhance the overall HDN reaction to provide a more substantial conversion to substituted benzene and aniline derivatives. (2) The dramatic effect of the nitrogen atom is to inhibit aromatic ring hydrogenation and, to some extent, carbon-carbon bond hydrogenolysis reactivity. This is shown with proplybenzene as the substrate, where only methane gas is produced in the HDN reaction with the 50% nickel oxide catalyst. (3) The HDN ...
A process is claimed for selectively preparing alpha-olefins having from 2 to about 22 carbon atoms by contacting a gaseous mixture containing carbon monoxide and hydrogen with an iron titanate alkali metal hydroxide catalyst at reaction conditions correlated so as to favor the formation of a substantial proportion of such alpha-olefin product.
Top quark is extremely sensitive to non-standard CP violating phases. General strategies for exposing different types of phases at the NLC are outlined. SUSY phase(s) cause PRA in $t\\to Wb$. The transverse polarization of the $\\tau$ in the reaction $t\\to b\\tau\
The oxidation of CO over a Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was studied by cyclic injection of CO and O{sub 2} pulses under CO and O{sub 2} pressures of 2 and 1 kPa, respectively, at temperatures of 330-650 K. A boundary reaction model yielded kinetic parameters in agreement with the results of published low-pressure studies. For CO{sub 2} formation from O{sub 2}(g) + (CO){sub ad}, CO desorption was the most important step and showed multipeak characteristics and a low activation energy (10 kJ/mol) for the boundary reaction was found. CO{sub 2} formation from O{sub 2}(g) + (CO) as well as from CO(g) + (O){sub ad} resulted from boundary reaction at oxygen island. A reaction mechanism was proposed to account for kinetics observed and interpret the varying observations noted in low-pressure studies in terms of diffusion-disguised kinetics.
An assay to measure the rate of enzymatic formation of 3-methylindole (3MI) from indoleacetic acid (IAA) in Lactobacillus sp. strain 11201 was developed. The reaction mixture contained 50 micrograms...Full Text Available
A short, highly stereoselective (over 97%) synthesis of all-trans squalene is described. Starting with succinaldehyde, a tetraenedichlorodione having the complete squalene skeleton...Full Text Available
The use of complementary and alternative medicines is becoming increasingly popular in Western society. As a result the number of reported adverse reactions is increasing. Glucosamine is a herbal remedy...Full Text Available
BackgroundGenotyping analysis using capillary DNA sequencing with fluorescently labeled primer pairs obtained by polymerase chain reaction (PCR) is widely used, but is expensive....Full Text Available