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  • oxidation  (49)
  • Springer  (49)
  • American Meteorological Society
  • Blackwell Publishing Ltd
  • Cambridge University Press
  • 1995-1999  (49)
  • 1996  (49)
Collection
Keywords
Publisher
  • Springer  (49)
  • American Meteorological Society
  • Blackwell Publishing Ltd
  • Cambridge University Press
  • Wiley-Blackwell  (9)
Years
  • 1995-1999  (49)
Year
  • 1
    Electronic Resource
    Electronic Resource
    Purification and characterization of fumarase from the syntrophic propionate-oxidizing bacterium strain MPOB (1996)
    Springer
    Archives of microbiology 165 (1996), S. 126-131 
    Details
    ISSN: 1432-072X
    Keywords: Key words Fumarase ; Syntrophy ; Propionate ; oxidation ; Fumarate fermentation ; Anaerobic oxidation ; Iron-sulfur cluster
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Fumarase from the syntrophic propionate-oxidizing bacterium strain MPOB was purified 130-fold under anoxic conditions. The native enzyme had an apparent molecular mass of 114 kDa and was composed of two subunits of 60 kDa. The enzyme exhibited maximum activity at pH 8.5 and approximately 54° C. The K m values for fumarate and l-malate were 0.25 mM and 2.38 mM, respectively. Fumarase was inactivated by oxygen, but the activity could be restored by addition of Fe2+ and β-mercaptoethanol under anoxic conditions. EPR spectroscopy of the purified enzyme revealed the presence of a [3Fe-4S] cluster. Under reducing conditions, only a trace amount of a [4Fe-4S] cluster was detected. Addition of fumarate resulted in a significant increase of this [4Fe-4S] signal. The N-terminal amino acid sequence showed similarity to the sequences of fumarase A and B of Escherichia coli (56%) and fumarase A of Salmonella typhimurium (63%).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s002030050307
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  • 2
    Electronic Resource
    Electronic Resource
    Synergistic effects during CO oxidation over mixed oxides. Study of (Fe2O3+SnO2) and (Mn2O3+SnO2) systems (1996)
    Springer
    Catalysis letters 37 (1996), S. 181-185 
    Details
    ISSN: 1572-879X
    Keywords: synergistic effect ; carbon monoxide ; oxidation ; mixed oxides ; iron oxide ; tin oxide ; manganese oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Based on the comparative evaluation of the catalytic activity of Fe2O3, Mn2O3 and SnO2 and their mixed oxides (Fe2O3+SnO2) and (Mn2O3+SnO2), it is shown that the system (Mn2O3+SnO2) shows strong synergistic effects during CO oxidation reaction. Such effects are not observed for the analogous system (Fe2O3+SnO2). Based on the calcination and reduction behaviour of these two mixed oxide systems and the redox potentials of the involved cations, the possible reasons for the observance of synergistic effects for the (Mn2O3+SnO2) system are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00807751
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  • 3
    Electronic Resource
    Electronic Resource
    Oxidative dehydrogenation of ethane over La1−xSrxFeO3−δ perovskite oxides (1996)
    Springer
    Catalysis letters 38 (1996), S. 189-195 
    Details
    ISSN: 1572-879X
    Keywords: perovskite ; La1−xSrxFeO3−δ ; dehydrogenation ; oxidation ; ethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Catalysts of the composition La1−xSrxFeO3−δ, 0⩽x ⩽1, have been tested for the oxidative dehydrogenation of ethane in the temperature range 300–800°C. The catalyst is active above 400°C, giving a maximum yield of 37% ethylene at 650°C. Above 650°C, synthesis gas was formed together with methane, suggesting that the reforming reaction and thermal cracking of ethane took place. The catalytic data are compared to conductivity measurements on the same material, and a good correlation between the activity and p-type conductivity has been found. In the phase diagram for the system LaFeO3-SrFeO3−δ, a phase separation to two types of (La, Sr)FeO3−δ perovskites was observed in the La/Sr binary composition in the temperature range below 800°C. The phase separation can elucidate the dependency of the catalytic activity on its p-type conductivity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00806567
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  • 4
    Electronic Resource
    Electronic Resource
    Non-uniform surface kinetics with two types of sites: the case of ethanol oxidation on molybdenum oxide (1996)
    Springer
    Catalysis letters 39 (1996), S. 67-71 
    Details
    ISSN: 1572-879X
    Keywords: non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00813732
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  • 5
    Electronic Resource
    Electronic Resource
    Inhibition of CO oxidation on hydroxyapatite by tetrachloromethane (1996)
    Springer
    Catalysis letters 39 (1996), S. 205-208 
    Details
    ISSN: 1572-879X
    Keywords: oxidation ; hydroxyapatite ; carbon monoxide ; inhibition ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The introduction of tetrachloromethane (TCM) into the feedstream of CO and O2 inhibits the formation of CO2 on hydroxyapatite. TCM interacts with the surface of hydroxyapatite to form its chlorinated analogue, chlorapatite, which suppresses the oxidation of CO to CO2. Thus, in the oxidative coupling of methane the beneficial effects of the addition of TCM to the feedstream result, at least in part, from the suppression of the further oxidation of CO.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00805584
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  • 6
    Electronic Resource
    Electronic Resource
    Oxidation of methanol at copper surfaces (1996)
    Springer
    Catalysis letters 37 (1996), S. 79-87 
    Details
    ISSN: 1572-879X
    Keywords: methanol ; oxidation ; copper ; electron spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The role of preadsorbed oxygen present at Cu(111), Cu(110) and polycrystalline surfaces in the oxidation of methanol has been investigated by X-ray and electron energy loss spectroscopies. In addition to the well established formation of methoxy species and its subsequent decomposition and desorption as formaldehyde, a second reaction pathway to surface formate is present. The latter is temperature dependent being undetectable at 260 K at a polycrystalline surface but occurs at a significant rate at 295 K and above. The limitations of experimental data for methanol oxidation by temperature programmed desorption and molecular beam techniques are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00813523
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  • 7
    Electronic Resource
    Electronic Resource
    Catalytic oxidation of cyclohexene with molecular oxygen by polyoxometalate-intercalated hydrotalcites (1996)
    Springer
    Catalysis letters 40 (1996), S. 43-45 
    Details
    ISSN: 1572-879X
    Keywords: oxidation ; cyclohexene ; polyoxometalate-intercalated hydrotalcite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cyclohexene was oxidized with molecular oxygen over transition-metal-substituted polyoxometalate-intercalated hydrotalcites to produce 2-cyclohexene-1-one and 2-cyclohexene-1-ol with high selectivity under mild reaction conditions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00807455
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  • 8
    Electronic Resource
    Electronic Resource
    Selective oxidation of secondary amines over titanium silicalite molecular sieves, TS-1 and TS-2 (1996)
    Springer
    Catalysis letters 37 (1996), S. 213-216 
    Details
    ISSN: 1572-879X
    Keywords: titanium silicalites ; oxidation ; amines ; hydrogen peroxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Titanium silicalite molecular sieves, TS-1 and TS-2 having MFI and MEL structures, respectively, catalyze the oxidation of secondary amines to the corresponding hydroxylamines using hydrogen peroxide as the oxidant. Higher concentrations of H2O2 lead to further oxidation of hydroxylamine to nitrone. Diffuse reflectance spectroscopy shows the formation of a titanium peroxo complex upon addition of hydrogen peroxide to the TS-1 catalyst. The titanium peroxo complex oxidizes the substrate and reforms to a titanyl group.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00807756
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  • 9
    Electronic Resource
    Electronic Resource
    Baeyer-Villiger rearrangement catalysed by titanium silicate molecular sieve (TS-1)/H2O2 system (1996)
    Springer
    Catalysis letters 40 (1996), S. 47-50 
    Details
    ISSN: 1572-879X
    Keywords: Baeyer-Villiger ; titanium silicate molecular sieve ; oxidation ; rearrangement ; titanium peroxo ; triphase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Titanium silicate molecular sieve TS-1 has been found to be an efficient catalyst for Baeyer-Villiger (BV) oxidation of cyclic and aromatic ketones under triphase conditions (solid catalyst along with two immiscible liquid reactants in the absence of any cosolvent), using dilute H2O2. Reactions studied are the oxidation of cyclohexanone and acetophenone. Whereas in the case of cyclohexane,ε-caprolactone, a BV product along with hydroxy and diketones is formed, in the case of acetophenone, phenyl acetate, a BV product along witho- andp-hydroxyacetophenone is formed. The acidic nature of titanium peroxo species, stabilised by water, is proposed to be responsible for such reactions under triphasic reaction conditions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00807456
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  • 10
    Electronic Resource
    Electronic Resource
    Platinum particle size effect on the oxidative dehydrogenation of aqueous ethanol (1996)
    Springer
    Catalysis letters 36 (1996), S. 31-36 
    Details
    ISSN: 1572-879X
    Keywords: ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00807202
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  • 11
    Electronic Resource
    Electronic Resource
    Perfluoroalkylporphyrin complexes as active catalysts for the reaction of isobutane with oxygen and the decomposition of tert-butyl hydroperoxide (1996)
    Springer
    Catalysis letters 36 (1996), S. 69-73 
    Details
    ISSN: 1572-879X
    Keywords: oxidation ; metalloporphyrins ; hydroperoxide decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new family of metalloporphyrin complexes having perfluoroalkyl groups in the meso-positions of the ring are active catalysts for the oxidation of isobutane to tert-butyl alcohol, TBA, and for the decomposition of tert-butyl hydroperoxide to TBA. This discovery extends the limited number of meso-substituents that can be used to enhance catalytic activity and fits the postulate that groups that withdraw electrons from the porphyrin periphery give rise to active catalysts for alkane oxidation. The perfluoroalkyl groups also confer oxidative stability, hydrophobicity and lower cost to the catalyst.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00807207
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  • 12
    Electronic Resource
    Electronic Resource
    A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation using dioxygen as the oxidant (1996)
    Springer
    Catalysis letters 40 (1996), S. 95-99 
    Details
    ISSN: 1572-879X
    Keywords: palladium metal ; oxidation ; toxic organics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In water, metallic palladium was found to catalyze the deep oxidation of a wide variety of functional organics by dioxygen at 80–90°C in the presence of carbon monoxide. Several classes of organic compounds were examined: benzene, phenol and substituted phenols, aliphatic and aromatic halogenated compounds, organophosphorus, and organosulfur compounds. In every case, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 h period. Since the heterogeneous catalyst can be removed by simple filtration, simultaneous water purification and contaminant destruction becomes feasible. For those substrates that are insoluble in pure water, a mixture of water and perfluorobutyric acid was successfully employed as the solvent.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00807463
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  • 13
    Electronic Resource
    Electronic Resource
    Influence of external mechanical loadings (creep, fatigue) on oxygen diffusion during nickel oxidation (1996)
    Springer
    Oxidation of metals 45 (1996), S. 153-181 
    Details
    ISSN: 1573-4889
    Keywords: oxidation ; 18O diffusion ; nickel ; stress effects on diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This study deals with the influence of various mechanical loadings (fatigue, creep, creep-fatigue) on oxygen diffusion in a particular system, oxidizing nickel. A distinction between the behavior of the oxide layer and underlying nickel was noted during the first step of oxidation at 550°C, in PO 2=1 atm. Mechanical loading causes a decrease of the oxygen mobility through the oxide scale (factor of 103). The oxide thicknesses on nickel undergoing mechanical loadings are different than for an unloaded sample, due to distinct contributions of the oxygen and nickel fluxes in the growing oxide. In the substrate, the ingress of oxygen becomes easier with a constant tensile load (creep). The intergranular-oxygen diffusion coefficient, Di, is increased by a factor of 102 with respect to other samples. In creep, oxygen diffusion takes place along grain boundaries of a structure with smaller grains than in unstrained Ni. A short fatigue period during creep-fatigue decreases the sensitivity of nickel to intergranular-oxygen diffusion.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01046824
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  • 14
    Electronic Resource
    Electronic Resource
    High-temperature corrosion of Ti and Ti-6Al-4V alloy (1996)
    Springer
    Oxidation of metals 45 (1996), S. 507-527 
    Details
    ISSN: 1573-4889
    Keywords: oxidation ; sulfidation ; oxides ; sulfides ; Ti ; Ti-6Al-4V alloy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Pure titanium and Ti-6Al-4V were exposed at 750°C in an H2/H2O/H2S PO 2≈10−18 Pa and PS 2≈10−1 Pa), H2/H2O (PO 2≈10−18 Pa) and air environments for up to 240 hr. The corrosion kinetics, obtained by the discontinuous gravimetric method, showed that the sulfidation/oxidation kinetics were linear for Ti and linear-parabolic for Ti-6Al-4V in the H2/H2O/H2S environment. Both materials obeyed parabolic rate laws in the H2/H2O atmosphere after a transient period, and linear-parabolic rate laws in air. After exposure to the H2/H2O/H2S atmosphere, the titanium specimen displayed a double scale of TiO2 with an intervening TiS2 film between the double-layered scale of TiO2 and the substrate. Ti-6Al-4V also contained a double layer of TiO2 together with a stratum consisting of Al2S3, TiS2 and vanadium sulfide at the junction of the inner TiO2 layer and substrate. Some Al2O3 precipitated in the external portion of the outer TiO2 layer. Following oxidation in the low-PO 2 atmosphere a double-layered oxide of TiO2 scale formed on both Ti and Ti-6Al-4V. The scale on Ti-6Al-4V also contained an α-Al2O3 film situated between the outer and inner (TiO2) layers. For both materials, multilayered-scale formation characterized air oxidation. In detail a multilayered oxide scale of TiO2 formed on the air-oxidized Ti, while a multilayered oxide scale with alternating layers of Al2O3/TiO2 developed on Ti-6Al-4V oxidized in air.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01046849
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  • 15
    Electronic Resource
    Electronic Resource
    Mixed oxidant corrosion in nonequilibrium gasifier environments (1996)
    Springer
    Oxidation of metals 45 (1996), S. 487-505 
    Details
    ISSN: 1573-4889
    Keywords: sulfidation ; oxidation ; gasification ; austenitic steel alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The major use of high-temperature steel alloys in gasifiers is in heat exchangers for cooling hot syngas, consisting mainly of CO and H2 with lesser amounts of H2O and CO2 and minor quantities of H2S and HCl. Metal temperatures range from 250 to 600°C, gas temperatures from 250 to 1200°C. Because of rapid cooling the composition of the gas does not change with temperature. Therefore the gas is not in equilibrium at the metal surface. Calculations show that such gases have lower oxygen and sulfur pressures than equilibrated gases at the same temperature. This makes the results of previous laboratory studies less appropriate for predicting mixed oxidant corrosion in gasifiers. For this reason the present study was carried out using nonequilibrium gas mixtures, similar to gases, produced in entrained-slagging gasifiers. Most corrosion experiments were carried out at 540°C, as this is a common temperature for superheaters and hot-gas cleanup systems. Iron-base model alloys containing 35% Ni, 20% Cr, and various minor alloying additions were studied. Three corrosion regimes were identified over the range of conditions studied, depending on the sulfur-to-oxygen pressure ratio of the gas and the alloy composition. At high PS 2/PO 2 ratios a somewhat protective FeCr2S4 scale formed on all alloys. Below this layer internal oxidation and sulfidation occurred at a slow rate. At lower PS 2/PO 2 ratios nonprotective Fe(Ni, Cr)S external scales formed. These allow rapid internal oxidation of the chromium in the alloy, resulting in high corrosion rates. Under the same conditions very low corrosion rates are obtained when silicon is added to the alloy, because the presence of SiO2 precipitates makes the internal-oxidation layer protective. Thus, the same corrosion model is operative in all three corrosion regimes: external sulfidation of iron and nickel, together with internal oxidation of chromium and other strong-oxide formers.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01046848
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  • 16
    Electronic Resource
    Electronic Resource
    Effect of short-circuiting on the oxidation kinetics of copper and its doped varieties in the temperature range of 523–1073 K (1996)
    Springer
    Oxidation of metals 46 (1996), S. 73-107 
    Details
    ISSN: 1573-4889
    Keywords: oxidation ; copper ; Li-doped copper ; Cr-doped copper ; short-circuiting ; Mott's parabola ; Wagner's parabola
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of shorting circuitry attachment between metal-oxide and oxideoxygen interfaces on the oxidation kinetics of copper, lithium-doped copper (Li: 400 ppm), and chromium-doped copper (Cr: 12 ppm) have been studied in dry air $$(P_{O_2 } = 21.27kPa)$$ in the temperature range of 523–1073 K. Oxide film or scale growth under short-circuiting as well as under normal oxidation conditions conforms to the parabolic rate law. The oxidation kinetics under short-circuiting resulted in decreased rates for Cu and Li-doped Cu up to a temperature of 773 K, while Cr-doped Cu exhibited an enhancement in rate compared to its normal oxidation in the same temperature range. However, above 873 K, all three systems under shorting circuitry attachment exhibited enhanced rates compared to their normal oxidation rates in conformity to the existing theoretical model. Use of additional resistances in series in the outer short-circuit Pt path have clearly established that below 773 K Mott's fieldinduced migration plays the most important role, while at elevated temperatures Wagner's electrochemical potential-gradient factor acts as the main driving force in the scale-growth process. The results have been interpreted on the basis of average defect concentration, the electrochemical potential gradient, electrical field gradient, and transport coefficient in the Cu2O layer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01046885
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  • 17
    Electronic Resource
    Electronic Resource
    Effect of Cr, Co, and Ti additions on the high-temperature oxidation behavior of Ni3Al (1996)
    Springer
    Oxidation of metals 46 (1996), S. 109-127 
    Details
    ISSN: 1573-4889
    Keywords: oxidation ; Ni3Al base alloy ; chromium ; cobalt ; titanium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of Ni3Al+2.90 wt.% Cr, Ni3Al+3.35 wt% Co, and Ni3Al+2.99 wt.% Ti alloys was studied in 1 atm of air at 1000, 1100, and 1200°C. Isothermal tests revealed parabolic kinetics for all three alloys at all temperatures. Cyclic oxidation for 28 two-hour cycles produced little spallation at 1000°C, but caused partial spallation at 1100°C. Especially, at 1200°C severe spallation in all three alloys was observed. Although additions of Cr, Co, or Ti to Ni3Al alloys slightly increased the isothermal-oxidation resistance, the additions tended to decrease the cyclic-oxidation resistance. The major difference in the oxidation of the three alloys compared with the oxidation of pure Ni3Al alloys was the existence of small α-Al2O3 particles in the middle of the α-Al2O3 scale and the formation of irregularly shaped Kirkendall voids at the alloy-scale interface.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01046886
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  • 18
    Electronic Resource
    Electronic Resource
    TEM investigations of the early stages of TiAl oxidation (1996)
    Springer
    Oxidation of metals 46 (1996), S. 255-285 
    Details
    ISSN: 1573-4889
    Keywords: electron diffraction ; intermetallic ; oxidation ; TEM ; titanium aluminide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The early stages of TiAl oxidation at 900°C and 1000°C in air have been investigated by transmission electron microscopy (TEM). The investigations revealed that at the beginning of oxidation, i.e., after 4 min, TiO2 and Al2O3 grow in a preferential orientation on the γ-TiAl substrate. After 4 h of oxidation an oxide scale structure can already be found similar to that known from long-term oxidation. In addition, besides α-Al2O3, the formation of a second aluminum oxide phase and of titanium nitrides is observed. The processes at the metal-oxide interface of oxidation in the early stages, consisting of a repeated cycle of Al2O3 formation, Al2O3 dissolution, outward migration of Al through the scale, and reprecipitation of Al2O3 in the outer scale, are described by a model. The four stages observed in the kinetics of TiAl oxidation are explained on the basis of the results obtained and the structure of the oxide scale.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01050799
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  • 19
    Electronic Resource
    Electronic Resource
    Effects of Polyaminocarboxylate Metal Chelators on Iron-thiolate Induced Oxidation of Methionine- and Histidine-Containing Peptides (1996)
    Springer
    Pharmaceutical research 13 (1996), S. 931-938 
    Details
    ISSN: 1573-904X
    Keywords: iron ; chelator ; oxidation ; methionine/histidine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Site-specific protein oxidation induced by prooxidant/metal/ oxygen has been recognized as one of the major degradation pathways of protein pharmaceuticals. Polyaminocarboxylate (PAC) metal chelators are commonly employed to prevent metal-catalyzed oxidation, for they sequester metals. However, studies have indicated that iron chelates may still be catalytically active due to their specific coordination geometry. The purpose of this study was to investigate how PAC chelators affect prooxidant/metal/oxygen-catalyzed oxidation of peptides containing histidine (His) and methionine (Met). Methods. PACs were applied to a model oxidizing system, dithiothreitol/iron/oxygen, which was shown to promote the oxidation of Met to Met sulfoxide in the two model peptides, GGGMGGG and GHGMGGG. Results. PAC chelators did not suppress the peptide oxidation but significantly changed the product pattern. In particular, the yield of Met sulfoxide dropped significantly, while a number of other products emerged, including oxidation products from the N-terminus and His (if present). Overall, the oxidation became rather non-selective in the presence of PACs. The oxidation kinetics were significantly accelerated by nitrilotriacetate (NTA), ethylenediaminediacetate (HDDA), and ethylenediaminetetraacetate (EDTA), but they were slowed down by ethyl-enebis(oxyethylenenitrilo)tetraacetate (EGTA) and diethylenetriaminepentaacetate (DTPA). Meanwhile the PAC chelators were also observed to undergo degradation. Scavengers of hydrogen peroxide or hydroxyl radicals exerted only partial inhibition on the peptide oxidation. Conclusions. The results of this study are rationalized by the abilities of PAC chelators (i) to extract iron from potential binding sites of the peptides to impair site-specific oxidation, and (ii) to promote the formation of ROS different from the species formed at the peptide metal-binding sites.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1016021716274
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  • 20
    Electronic Resource
    Electronic Resource
    Stability of a molybdena-silica catalyst enhanced by water in formaldehyde oxidation (1996)
    Springer
    Reaction kinetics and catalysis letters 58 (1996), S. 323-328 
    Details
    ISSN: 1588-2837
    Keywords: Formaldehyde ; oxidation ; molybdena ; methanol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A molybdena-silica catalyst showed rapid deactivation in the oxidation of formaldehyde to carbon oxides. The deactivation was greatly retarded by adding water in the feed. Thus, water coproduced in the partial oxidation of methanol to formaldehyde contributes to the relatively stable activity of the molybdena-silica catalyst in the partial oxidation reaction.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02067040
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  • 21
    Electronic Resource
    Electronic Resource
    Oxidative dehydrogenation of propane (1996)
    Springer
    Reaction kinetics and catalysis letters 57 (1996), S. 3-11 
    Details
    ISSN: 1588-2837
    Keywords: Dehydrogenation ; oxidation ; propane ; propylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract At temperatures near 650°C and residence times ofca. 3 s, the homogeneous oxidative dehydrogenation (OXD) of propane to propylene and ethylene approached oxygen limiting conditions, even when the reactor was filled with quartz chips. The addition of catalysts that are known to be effective in the OXD of ethane slightly increased the reaction rate, but the selectivities at a given conversion level were the same as those that were achieved in the homogeneous reaction.
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    URL: http://dx.doi.org/10.1007/BF02076113
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    Fundamental studies on the development of lignin-based adhesives, I. Catalytic demethylation of anisole with molecular oxygen (1996)
    Springer
    Reaction kinetics and catalysis letters 58 (1996), S. 237-242 
    Details
    ISSN: 1588-2837
    Keywords: Iron porphyrin catalyst ; oxidation ; lignin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In the presence of a catalyst consisting of metal-porphyrin complex and a reductant, anisole was converted into phenol by molecular oxygen at room temperature with a total turnover of the catalyst of about 70 times in 24 h.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02067028
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    Kinetic analysis of DSC and thermogravimetric data on combustion of lignite (1996)
    Springer
    Journal of thermal analysis and calorimetry 46 (1996), S. 1657-1669 
    Details
    ISSN: 1572-8943
    Keywords: activation energy ; combustion ; differential scanning calorimetry ; kinetics ; lignite ; oxidation ; thermogravimetric analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis increasingly being used to obtain kinetic data relating to sample decomposition. This work involves a comparative study of several methods used to analyse DSC and TG/DTG data obtained on the oxidation of Beypazari lignite. A general computer program was developed and the methods are compared with regard to their accuracy and the ease of interpretation of the kinetics of thermal decomposition. For this study, the ratio method was regarded as the preferred method, because it permits the estimation of reaction order, activation energy and Arrhenius constant simultaneously from a single experiment.
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    URL: http://dx.doi.org/10.1007/BF01980771
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    Reassessment of the roles of the peritrophic envelope and hydrolysis in protecting polyphagous grasshoppers from ingested hydrolyzable tannins (1996)
    Springer
    Journal of chemical ecology 22 (1996), S. 1901-1919 
    Details
    ISSN: 1573-1561
    Keywords: Orthoptera ; Acrididae ; grasshopper ; Melanoplus sanguinipes ; Phoetaliotes nebrascensis ; peritrophic envelope ; peritrophic membrane ; hydrolyzable tannin ; tannic acid ; oxidation ; hydrolysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract We examined several of the mechanisms that have been reported to enable polyphagous grasshoppers (Orthoptera: Acrididae) to tolerate ingested hydrolyzable tannins: hydrolysis, adsorption on the peritrophic envelope, and peritrophic envelope impermeability. None of these mechanisms explain the tolerance ofMelanoplus sanguinipes to ingested tannic acid. In this species, tannin hydrolysis was 12–47% complete, adsorption accounted for less than 1% of the tannic acid contained in the midgut, and the peritrophic envelope was permeated by several gallotannins. The foregut is the main site for the chemical transformation of tannic acid in this species. InPhoetaliotes nebrascensis, hydrolysis was more extensive (82% complete), but the peritrophic envelope was readily permeated by two gallotannins. Oxidizing redox conditions were found in the guts of both species, and ingested tannins were oxidized inM. sanguinipes. We hypothesize that the tolerance of some polyphagous grasshoppers to ingested hydrolyzable tannins may be the consequence of their ability to tolerate the reactive oxygen species generated by polyphenol oxidation, whereas others may rely on rapid and extensive hydrolysis.
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    URL: http://dx.doi.org/10.1007/BF02028511
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    The corrosion of pure niobium in oxidizing, sulfidizing, and oxidizing-sulfidizing gas mixtures at 600–800°C (1996)
    Springer
    Oxidation of metals 46 (1996), S. 287-297 
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    ISSN: 1573-4889
    Keywords: pure niobium ; oxidation ; sulfidation ; oxidation-sulfidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion of pure niobium has been studied at 600–800°C in various environments as part of a study of the corrosion resistance of its alloys with iron, cobalt, and nickel to atmospheres of low-oxygen and/or high-sulfur activities. The results have shown that not only the sulfidation but also the corrosion in mixed atmospheres and particularly the oxidation under low oxygen pressures of pure niobium are quite slow, with kinetics rather similar in the three types of gas mixtures used. The good corrosion resistance of niobium to attack by oxygen under low pressures is quite interesting because this element is corroded very rapidly by oxygen under high oxygen pressures, due to the formation of the nonprotective highest oxide Nb2O5 as a main corrosion product.
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    URL: http://dx.doi.org/10.1007/BF01050800
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    The oxidation behavior of Fe-20Cr alloy foils in a synthetic exhaust-gas atmosphere (1996)
    Springer
    Oxidation of metals 46 (1996), S. 335-364 
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    ISSN: 1573-4889
    Keywords: Fe−Cr ; oxidation ; exhaust gas ; oxide adherence ; titanium ; rare earths
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation tests of rare-earth-modified and Ti-modified Fe−20Cr alloy foils, which are under consideration for catalytic converter supports, were performed in a synthetic exhaust-gas atmosphere (N2+H2O+CO2) between 900°C and 650°C. Between 900°C and 750°C, the rare earths had no effect on oxide growth rates while Ti increased growth rates. Oxide growth rates for the rareearth alloys at 800°C and 750°C are much lower than those found in the literature for oxidation of Fe−Cr alloys or pure Cr in O2-rich atmospheres. The slow growth rates for the rare-earth alloys agree with literature data for oxidation of stainless steels containing 〉20% Cr in wet atmospheres and are caused by growth of an oxide scale only one grain thick. At temperatures ≤700°C, Fe−20Cr alloys grow massive Fe oxides; however, this can be suppressed by adding rare earths or Ti. To ensure good oxide adherence, free sulfur must be eliminated in the alloy by tying it up with a reactive-element addition. Both Ti and the rare earths can be used to tie up S, but the rare earths are more effective. For converter applications, the optimum alloy composition may contain rare earths for good oxide adherence and a small amount of Ti to suppress growth of Fe-rich oxides.
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    URL: http://dx.doi.org/10.1007/BF01048635
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    Transient oxidation in Fe-Cr-Ni alloys: A Raman-scattering study (1996)
    Springer
    Oxidation of metals 46 (1996), S. 365-381 
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    ISSN: 1573-4889
    Keywords: oxidation ; steel ; Raman ; scale ; transient oxides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Using Raman scattering we have investigated the oxidation, in air, of the Fe-Cr-Ni stainless steels Fe-25Cr-20Ni, Fe-25Cr-20Ni-3Zr, and Fe-24Cr-3Zr (wt.%) as a function of temperature in the range 300 to 1000°C. The Raman technique is very sensitive to, and provides a clear identification of, the oxides Fe2O3 and Cr2O3. However, the technique is insensitive to NiO, FeO, and does not give a clear identification of spinels. The Fe−Cr−Ni alloys form chromia scales at temperatures greater than ∼800°C. At lower oxidation temperatures, transient phases are observed. With a 1-h heat treatment at 300°C, we observe the formation of an unidentified scale; we speculate that it is either amorphous or consists of disordered spinel(s). Near 400°C we begin to observe hematite (Fe2O3). The intensity of the Fe2O3 signal increases with temperature to ∼600°C and then decreases, being largely replaced by the signal from Cr2O3. The thickness of the Cr2O3 scale increases with temperature up to ∼1000°C above which spallation becomes apparent. Spinel phases also apparently persist in the scale to 1000°C.
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    URL: http://dx.doi.org/10.1007/BF01048636
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    The steady-State corrosion kinetics of two-phase binary alloys forming the most-stable oxide (1996)
    Springer
    Oxidation of metals 46 (1996), S. 383-398 
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    ISSN: 1573-4889
    Keywords: high temperatures ; binary alloys ; two-phase alloys ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The steady-state kinetics in the high-temperature oxidation of binary A-B alloys containing a mixture of the conjugated solid solutions of B in A (alpha phase) and A in B (beta phase) with exclusive formation of the most-stable oxide BOv have been examined, assuming that the external scale grows on top of a subsurface layer of alpha phase. The results obtained are compared with the corresponding behavior of alloys which are single phase in the whole range of composition. Under identical values of all the parameters involved the concentration of B at the alloy-scale interface is smaller for two-phase than for single-phase alloys under the same concentration of B in the alloy as a result of the restricted flux of B through the alpha-phase layer. As a consequence of this, the two-phase alloys corrode more slowly than single-phase alloys and this difference increases as the solubility of B in the alpha phase decreases. Finally, the simultaneous formation of BOv both externally and as internal oxide is more likely for two-phase than for single-phase materials.
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    An analysis of the internal oxidation of binary M-Nb alloys under low oxygen pressures at 600–800°C (1996)
    Springer
    Oxidation of metals 46 (1996), S. 441-463 
    Details
    ISSN: 1573-4889
    Keywords: niobium alloys ; oxidation ; high temperatures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The corrosion of M−Nb alloys based on iron, cobalt, and nickel and containing 15 and 30 wt% Nb has been studied at 600–800°C under low oxygen pressures (10−24 atm at 600°C and 10−20 atm at 700–800°C). Except for the Co−Nb and Ni−Nb alloys corroded at 800°C, which formed external scales of niobium oxides, corrosion under low O2 pressures produced an internal oxidation of niobium. This attack was much faster than expected on the basis of the classical theory. Furthermore, the distribution of the internal oxide in the alloys containing two metal phases was very close to that of the Nb-rich phase in the original alloys. These kinetic, microstructural, and thermodynamic aspects are examined by taking into account the effects of the limited solubility of niobium in the various base metals and of the two-phase nature of the alloys.
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    URL: http://dx.doi.org/10.1007/BF01048640
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    The effect of oxygen concentration on the oxidation of low-carbon steel in the temperature range 1000 to 1250°C (1996)
    Springer
    Oxidation of metals 46 (1996), S. 423-440 
    Details
    ISSN: 1573-4889
    Keywords: oxidation ; scaling ; surface temperature ; heat of reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper describes the oxidation behavior of low-carbon steel samples in binary gas mixtures of oxygen and nitrogen, at oxygen concentrations ranging between 1% and 15% and temperatures ranging between 1000 and 1250°C. Sample weight gains versus time were analyzed, along with measurements and calculations of sample heating rates due to exothermic heat of reaction at the sample surface. It was found that initial rates of oxidation depended on oxygen content in the gasmixture and that these reaction rates were linear up to oxide thicknesses of 0.4 to 0.5 mm. Calculations of linear oxidation rate constants based on equations for mass transport of oxygen in the gas mixture to the sample surface showed good agreement with those measured experimentally, indicating that the initial period of oxidation is controlled by the mass transport of oxygen to the reaction interface. The linear rate constants showed little dependency on temperature, an activation energy of approximately 17kJ/mole being obtained. Measurements of sample surface temperatures have shown that within this linear-oxidation regime, interfacial temperatures of the samples increase with increasing oxygen contents in the gas mixture, owing to exothermic heats of oxidation. Subsequent oxidation kinetics were found to be parabolic. Measured parabolic rates constants were in good agreement with previous investigations, with activation energy values of approximately 127kJ/mole.
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    URL: http://dx.doi.org/10.1007/BF01048639
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    Effect ofθ-alumina formation on the growth kinetics of alumina-forming superalloys (1996)
    Springer
    Oxidation of metals 46 (1996), S. 465-480 
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    ISSN: 1573-4889
    Keywords: ODS Alloy ; oxidation ; SIMS ; microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Alumina-forming ODS superalloys are excellent oxidation-resistant materials. Their resistance relies upon the establishment of a stable, slow-growing, and adherent α-alumina. In the present investigation, these alloys exhibited unstable and relatively less adherent θ-alumina phase, which increased the oxidation rate in the transient stage and converted into α-alumina in the later part of the exposure. The oxide-growth process was found to depend upon various parameters such as temperature, time, and presence of an active elecment in the superalloy. Characterization carried out by XRD, SEM/EDAX, and AES on oxidized ODS and non-ODS alloys demonstrated a significant influence of the active element, Y, on the transformation of θ- to α-alumina. SIMS analysis of two-stage oxidation at 900°C for two different durations evidently showed that the change in the transport process is due to θ-to-α-alumina transformation. On the basis of these results, a new and consistent mechanism is proposed to explain the influence of θ-alumina and its transformation on growth kinetics and the effect of yttrium on the transformation leading to good scale adherence and oxidation resistance.
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    A study on the oxidation characteristics of cast irons containing aluminum (1996)
    Springer
    Oxidation of metals 45 (1996), S. 109-131 
    Details
    ISSN: 1573-4889
    Keywords: Fe−Al−C ; Fe−Al−Si−C ; inoculation ; scale ; characterization ; oxidation ; high temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Isothermal-oxidation characteristics of cast irons containing aluminum (5–15% Al) from 700 to 1000°C in air have been studied. In addition to massgain measurements, the morphology and composition of the oxide scales have been examined by SEM-EDX system and XRD analysis. A normal Fe−5Al−C alloy does not develop protective, adherent scales. Even the addition of misch metal and calcium silicide to such an alloy does not improve its oxidation resistance. But aluminum cast iron develops considerable oxidation resistance only when a sufficient quantity of silicon is also present in the alloy. Treatment of the alloy with misch, metal and calcium silicide together assists in protective scale formation. Among the alloys investigated Fe−15Al−Si−C treated with misch metal and calcium silicide shows minimum oxidation at 1000°C.
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    Corrosion of iron in sulfur dioxide at 0.1 MPa (1996)
    Springer
    Oxidation of metals 45 (1996), S. 469-486 
    Details
    ISSN: 1573-4889
    Keywords: iron ; sulfur dioxide ; oxidation ; tracer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The reaction of iron with sulfur dioxide at 0.1 MPa and 1073 K was studied. The composition and morphology of the scales, transport phenomena occurring in the growing scales, and kinetics of the process were investigated. Scanning electron microscopy and various techniques of X-ray analysis were used. The transport phenomena were studied by marker and by radiotracer techniques. The scales were composed of sulfide and oxides and grew by the outward diffusion of metal. It was concluded that the process initially took place through the reaction of iron with sulfur dioxide molecules. During the next stage of the process the reaction with sulfur dioxide molecules as well as with oxygen molecules is possible.
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    Contribution to the understanding of the parabolic oxidation mechanism of dilute alloys. Part I: Oxides with metal excess or oxygen deficit (1996)
    Springer
    Oxidation of metals 46 (1996), S. 1-17 
    Details
    ISSN: 1573-4889
    Keywords: dilute alloys ; oxidation ; Wagner-Hauffe rule
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Concerning the parabolic oxidation of alloys with a low content of a different valence element, we show that the Wagner-Hauffe valence approach contains some inaccuracies. This paper is devoted to the growth of an oxide MO with metal excess or oxygen deficit. The analytical processing consists in solving the differential equation connecting the point defect flux to the oxygen pressure. This equation has been solved analytically in the case where the foreign-element concentration is very high compared to that of the point defects in the pure oxide. On this assumption with a lower-valence dopant, as long as the oxide conductivity remains essentially electronic, the oxidation is limited only by the transport of ionic defects across the scale under the electric-potential gradient. Moreover, an increase of the dopant concentration may lead to an oxide exhibiting partial ionic conductivity. Consequently, the parabolic constant variations as a function of the dopant concentration is not monotonic, contrary to results published before. With a higher-valence dopant, the conductivity always remains electronic, and this result agrees with predictions based on the Wagner Hauffe approach, though the demonstrations are fundamentally different.
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    Formation of isomeric iodohydrins from terminal alkenes upon oxidation by a RuCl3-NaIO4 system (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 2813-2815 
    Details
    ISSN: 1573-9171
    Keywords: alkenes ; catalysis ; oxidation ; iodohydrins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract RuCl3-catalyzed periodate oxidation of alkenes affords isomeric iodohydrins.
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    Interaction of diphenyl sulfide with sulfuryl chloride (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 2668-2669 
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    ISSN: 1573-9171
    Keywords: diphenyl sulfide ; sulfuryl chloride ; oxidation ; chlorination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction of diphenyl sulfide with sulfuryl chloride was studied. Depending on the reaction conditions, it occurs either as chlorination of the aromatic ring or as oxidation to give sulfoxide.
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    Acid-catalyzed formation of free radicals in the reaction of hydroperoxides with ketones (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 340-345 
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    ISSN: 1573-9171
    Keywords: oxidation ; acid catalysis ; free radicals ; acetonitrile ; p-toluenesulfonic acid ; tert-butyl hydroperoxide ; cyclohexanone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of formation of free radicals in the cyclohexanone (CH)-tert-butylhydroperoxide (TBHP)-para-toluenesulfonic acid (PTSA) system in acetonitrile was studied. The stoichiometry of the reaction corresponds to the consumption of two TBHP molecules per ketone molecule, whereas the yield of free radicals is -20 % based on the TBHP reacted.
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    New heterocyclic system based on vinylsulfonylfluorobenzene and X-ray structural study of this compound (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 414-416 
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    ISSN: 1573-9171
    Keywords: 1,2,4,5-tetrafluoro-3,6-bis(vinylthio)benzerne ; 1,2,4,5-tetrafluoro-3,6bis(vinylsulfonyl)benzene ; 5,6-difluorobenzo-[a,d]-bis(3,3′-dihydro-1,1′-sulfonylallyl-4,4′-perhydroazine) ; oxidation ; allylamine ; X-ray structural study
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidation of 1,2,4,5-tetrafluoro-3,6-bus (vinylthio)benzene (1) affords 1,2,4,5-tetra fluoro3,6-bis(vinylsulfonyl)benzene (2) in 65 % yield. The reaction of compound 2 with allylamine gives a new heterocyclic compound, 5,6-difluorobenzo-[a,d]-bis(3,3′-dihydro-l,l′-sulfonylallyl-4,4′-perhydroazine) (3). This compound is the product of nucleophilic addition at the vinylsulfonyl group and intramolecular replacement of fluorine atoms of the benzene ring. The structure of compound 3 has been established by X-ray structural study.
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    The influence of low-temperature oxidation of active carbons by nitric acid on their physicochemical properties (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 1071-1077 
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    ISSN: 1573-9171
    Keywords: active carbons ; oxidation ; surface chemistry ; n-hexane ; water ; methanol ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of oxidation by nitric acid on the character of oxygen-containing functional surface groups and porous structure of active carbons is considered. Adsorption properties of the initial and oxidized carbons are studied using adsorption isotherms of vapor of n-hexane and polar substances (water and methanol).
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    Heat release kinetics in the reaction of decane with nitric acid (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 1883-1888 
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    ISSN: 1573-9171
    Keywords: decane ; nitric acid ; nitrogen dioxide ; oxidation ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the reaction of decane with nitric acid (25.07–75.53 %) at 57.8 to 119 °C in an acid-decane-gas triphasic system was studied. The main contribution to the rate of heat release is made by the oxidation of decane with nitrogen dioxide in the organic phase proceedingvia the mechanism of a degenerate branched-chain reaction. Nitration plays the role of a chain termination reaction. The acid phase is the source of NO2, whose content increases with oxidation. The equilibrium of the nitrogen dioxide distribution in the triphasic system was analyzed. The kinetic law of the reaction, the dependences of the reaction constants of the initial and catalytic stages on temperature and the acid phase composition were determined. The results allow one to calculate the rate of heat release in the decane-HNO3 system under any conditions of the process.
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    Phenazinee di-N-oxide radical cation and its reactions with hydrocarbons (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 1889-1895 
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    ISSN: 1573-9171
    Keywords: phenazine di-N-oxide ; radical cation ; hydrocarbons ; oxidation ; mechanism ; O2 effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The absorption spectra of phenazine di-N-oxide radical cation (OPO+·) in dichloromethane were recorded by the spectroelectrochemical method in the range from 300 to 700 nm. The reactions of the electrochemically generated OPO+· withpara-substituted toluenes, ethylbenzene, and cumene were studied. Using differential cyclic voltammetry, relative rate constants of reactions of OPO+· with substrates were determined; their correlations with σ+ para constants of substituents gives p = -2.7, which attests to the nonradical character of the reaction of OPO+· with RH. This conclusion is confirmed by the study of the effect of O2 on oxidation of ethylbenzene and cumene.
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    Organofluorine sulfur-containing compounds (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 153-155 
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    ISSN: 1573-9171
    Keywords: polyfluorinated thiophenols ; difluorochloromethane ; reactions ; aryldifluoromethyl sulfides ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Polyfluorinated aryldifluoromethyl sulfides have been obtained by treatment of polyfluorinated 4-X-substituted thiophenols with chlorodifluoromethane in an alkaline medium. Reactions of difluoromethylpentafluorophenyl sulfide with H2O2, KMnO4, and HNO3, giving the corresponding sulfoxide and sulfone, were studied.
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    Study of cool-Dame phenomena during self-ignition of methane-oxygen mixtures (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 2316-2320 
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    ISSN: 1573-9171
    Keywords: methane ; oxidation ; cool names ; kinetic simulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Experimental studies and kinetic simulation have shown that the formation of cool flames is as typical of oxidation of methane as of oxidation of its homologs. Phenomena peculiar to the cool-flame processes in closed systems are observed, namely, the region of a negative temperature coefficient of the reaction, single and double cool-flame flashes, two stage ignition, and light radiation in the range of luminescence of formaldehyde.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01435374
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  • 44
    Electronic Resource
    Electronic Resource
    Oxidation by a “H2O2-vanadium complex-pyrazine-2-carboxylic acid” reagent (1996)
    Springer
    Russian chemical bulletin 45 (1996), S. 2386-2388 
    Details
    ISSN: 1573-9171
    Keywords: metal complex catalysis ; oxidation ; hydrogen peroxide ; vanadium complexes ; alkanes ; activation of the C-H bond
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Lower alkanes (ethane, propane,n-butane,n-pentane) are readily oxidized in acetonitrile solvent by H2O2 with vanadate anion — pyrazine-2-carboxylic acid (PCA), as the catalyst at 75 °C and pressures of −3 atm to produce predominantly or exclusively ketones (aldehydes). Isobutane is transformed selectively intotert-butyl alcohol. The oxidation of cyclohexane at 26 °C in acetone or acetic acid is less efficient than in acetonitrile. The reaction does not occur intert-butyl alcohol.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01435388
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  • 45
    Electronic Resource
    Electronic Resource
    Oxidation of Human Insulin-Like Growth Factor I in Formulation Studies, II. Effects of Oxygen, Visible Light, and Phosphate on Methionine Oxidation in Aqueous Solution and Evaluation of Possible Mechanisms (1996)
    Springer
    Pharmaceutical research 13 (1996), S. 1476-1481 
    Details
    ISSN: 1573-904X
    Keywords: sulfur ; protein ; oxidation ; chemometrics ; phosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The oxidation of methionine in human Insulin-like Growth Factor I (hIGF-I) in aqueous solution was studied with respect to oxygen, visible light and sodium phosphate. Methods. Aqueous solutions of hIGF-I were prepared with different amounts of phosphate and dissolved oxygen. The solutions were stored either in darkness or exposed to artificial visible light. The oxidized hIGF-I was quantified by RP-HPLC. A two level full factorial experimental design, with two levels of each of the three factors studied, was used. Results. Oxidation was found to be positively correlated with light, oxygen content and, interestingly, phosphate. The increasing effect of phosphate on the oxidation appears not to originate from metal contaminants. The influence of both oxygen and phosphate increased with time. The pH dependence of oxidation indicated the formation of a phosphorylated sulfonium ion as an oxidation intermediate. A significant interaction effect between phosphate and visible light suggested participation of radicals. Conclusions. Factorial experiments provide a valuable tool when studying complex mechanisms with interacting factors. The oxidation of methionine in hIGF-I is significantly affected by light but also by the presence of phosphate buffer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1016015226211
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  • 46
    Electronic Resource
    Electronic Resource
    Nicanartine Improves in Vitro Resistance of Lipoproteins to Oxidation (1996)
    Springer
    Pharmaceutical research 13 (1996), S. 457-461 
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    ISSN: 1573-904X
    Keywords: nicanartine ; lipoprotein ; oxidation ; plasma binding
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The aim of this study is to investigate the plasma protein binding of nicanartine and to measure its antioxidant effect on lipoproteins. Methods. The blood binding was studied with an erythrocyte partitioning method and the lipoprotein oxidation with the conjugated dienes method. Results. Nicanartine was 24.7% LDL (low density lipoprotein)-bound and 29.2% AAG (alphal-acid glycoprotein)-bound. Nicanartine delayed but did not stop the oxidation of the three density classes of lipoprotein HDL (high density lipoprotein), LDL, VLDL (very low density lipoprotein). The addition of AAG to LDL in the conjugated dienes method decreased the nicanartine fraction bound to LDL and decreased its antioxidant effect. The decrease of nicanartine LDL-bound fraction and the decrease in antioxidant effect were not parallel. Conclusions. This suggested that (a) AAG-bound nicanartine dissociated to equilibrate the decrease in LDL-bound nicanartine consummed by oxidation, or (b) the oxidation conditions could involve chemical modifications of nicanartine and therefore modify its affinity for AAG.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1016013130445
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  • 47
    Electronic Resource
    Electronic Resource
    Oxidation of Human Insulin-like Growth Factor I in Formulation Studies: Kinetics of Methionine Oxidation in Aqueous Solution and in Solid State (1996)
    Springer
    Pharmaceutical research 13 (1996), S. 1252-1257 
    Details
    ISSN: 1573-904X
    Keywords: hIGF-I ; oxidation ; methionine ; HPLC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The aim of this work was to study the kinetics of oxidation of methionine in human Insulin-like Growth Factor I (hIGF-I)1 in aqueous solution and in the solid state by the aid of quantification of oxygen. Methods. The oxidized form of hIGF-I was characterized by tryptic peptide analysis, RP-HPLC and FAB-MS and quantified by RP-HPLC. The oxygen content was quantified polarographically by a Clark-type electrode. Results. Second-order kinetics with respect to amount of protein and dissolved oxygen was found to be appropriate for the oxidation of methionine in hIGF-I. The rate constants ranged from 1 to 280 M−1 month−l and had an activation energy of 95 (+/−4) kJ/mole. Light exposure, storage temperature and oxygen content were found to have a considerable impact on the oxidation rates. No significant difference in reaction rates was found for the oxidation of hIGF-I in aqueous solution or in the solid state. A method for decreasing the oxygen content in aqueous solution without purging is described. Conclusions. Polarographic quantification of dissolved oxygen makes it possible to establish the kinetics for oxidation of proteins. The oxidation of methionine in hIGF-I appears to follow second-order kinetics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1016032808039
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  • 48
    Electronic Resource
    Electronic Resource
    Oxidative Degradation of Antiflammin 2 (1996)
    Springer
    Pharmaceutical research 13 (1996), S. 250-255 
    Details
    ISSN: 1573-904X
    Keywords: antiflammin 2 ; oxidation ; stability ; degradation ; HPLC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To study the oxidation of the methionine residue of antiflammin 2 (HDMNKVLDL, AF2) as a function of pH, buffer concentration, ionic strength, and temperature using different concentrations of hydrogen peroxide and to determine the accessibility of methionine residue to oxidation. Methods. Reversed-phase high-performance liquid chromatography (RPHPLC) was used as the main analytical method in determining the oxidation rates of AF2. Calibration curves for AF2 and the oxidation product, methionine sulfoxide of AF2 (Met(O)-3-AF2), were constructed for each measurement using standard materials. Fast Atom Bombardment Mass Spectroscopy (FABMS) was used to characterize the product. Results. Met(O)-3-AF2 was the only oxidation product detected at pH 3.0 to 8.0. The oxidation rates were independent of buffer concentrations, ionic strength, and pH from 3.0 to 7.0. However, there was an acceleration of the rates at basic pHs, and small amounts of degradation products other than Met(O)-3-AF2 were observed in this alkaline region. Conclusions. Oxidation of methionine in AF2 does not cause the biological inactivation reported by other laboratories since this drug is relatively stable under neutral conditions in the absence of oxiding agent.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1016095131836
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  • 49
    Electronic Resource
    Electronic Resource
    Characterization of a Solid State Reaction Product from a Lyophilized Formulation of a Cyclic Heptapeptide. A Novel Example of an Excipient-Induced Oxidation (1996)
    Springer
    Pharmaceutical research 13 (1996), S. 1811-1814 
    Details
    ISSN: 1573-904X
    Keywords: peptide stability ; peptide formulation ; oxidation ; fibrinogen receptor antagonist ; mannitol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To elucidate the structure of a degradation product arising from a lyophilized formulation of a cyclic heptapeptide, and to provide a mechanism to account for its formation. Methods. Preparative HPLC was used to isolate the degradate in quantities sufficient for structural studies. A structure assignment was made on the basis of the compounds spectroscopic properties (UV, MS, NMR) and the results of amino acid analysis. Results. The degradate was identified as a benzaldehyde derivative arising from the oxidative deamination of an aminomethyl phenylalanine moiety. The extent of formation of this product is influenced by the amount of mannitol used as an excipient in the formulation. A mechanism is proposed whereby reducing sugar impurities in mannitol act as an oxidizing agent via the intermediacy of Schiff base adducts which subsequently undergo tautomerization and hydrolysis. Conclusions. Reducing sugar impurities in mannitol are responsible for the oxidative degradation of the peptide via a mechanism that involves Schiff base intermediates. This mechanism may be a potential route of degradation of other arylmethyl amines in mannitol-based formulations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1016024923002
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