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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European journal of nutrition 30 (1991), S. 29-45 
    ISSN: 1436-6215
    Keywords: advanced glycosylation endproducts (AGE) ; ag(e)ing ; aminoguanidine ; ascorbate ; autoxidation ; biomarker ; browning reaction ; chemical modification of proteins ; diabetes ; glycation ; glycoxidation ; nonenzymatic glycosylation ; oxidation ; Maillard reaction ; Aminoguanidin ; Ascorbat ; Autooxidation ; Biomarker ; Bräunungsreaktion ; chemische Veränderung vonProteinen ; Diabetes ; Glycosylierung ; Glycoxidation ; nichtenzymatische ; Glycosylierung ; Oxidation ; Maillardreaktion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Medicine
    Description / Table of Contents: Zusammenfassung Die Maillard- oder Bräunungsreaktion genannten Umsetzungen zwischen reduzierenden Zuckern und Eiweiß führen zur chemischen Zerstörung der Aminosäuren und zum Verlust der Proteinqualität während der Lebensmittelbearbeitung und -lagerung. Der vorliegende Beitrag zeigt Befunde auf, daß die Maillardreaktion auch im Gewebe des Menschen bei der Alterung von Proteinen mit langer biologischer Halbwertszeit auftritt. Die Konzentrationen an den sogenannten Amadori-Produkten, die im Initialstadium der Maillardreaktion aus Glucose und den Proteinen der Augenlinse oder dem Kollagen der Haut entstehen, erwiesen sich als relativ konstant, auch mit zunehmendem Alter. Die Produkte der Glycosylierung und nachfolgenden Oxidation der Proteine, auch Glycoxidationsprodukte genannt, häufen sich dagegen im Alter an, und zwar bei Diabetikern in vermehrtem Maße. Zu diesen Produkten gehören die Aminosäurenderivate N-(carboxymethyl)-lysin (CML), N-(carboxymethyl)-hydroxylysin (CMhL) sowie das fluoreszierende Quervernetzungsprodukt Pentosidin. Während diese Glycoxidationsprodukte in den Körpergeweben nur in Spuren vorkommen, gibt es deutliche Hinweise auf die Anwesenheit weiterer Bräunungsprodukte, deren Charakterisierung jedoch noch aussteht. Es werden Möglichkeiten zur „Entgiftung“ der reaktiven Zwischenprodukte aus der Maillardreaktion sowie zum Abbau extrem gebräunter Proteine diskutiert sowie neuere Möglichkeiten zur therapeutischen Modulierung fortgeschrittener Stadien der Maillardreaktion aufgezeigt.
    Notes: Summary The Maillard or browning reaction between reducing sugars and protein contributes to the chemical deterioration and loss of nutritional value of proteins during food processing and storage. This article presents and discusses evidence that the Maillard reaction is also involved in the chemical aging of long-lived proteins in human tissues. While the concentration of the Amadori adduct of glucose to lens protein and skin collagen is relatively constant with age, products of sequential glycation and oxidation of protein, termed glycoxidation products, accumulate in these long-lived proteins with advancing age and at an accelerated rate in diabetes. Among these products are the chemically modified amino acids, Nɛ-(carboxymethyl)lysine (CML), Nɛ-(carboxymethyl)hydroxylysine (CMhL), and the fluorescent crosslink, pentosidine. While these glycoxidation products are present at only trace levels in tissue proteins, there is strong evidence for the presence of other browning products which remain to be characterized. Mechanisms for detoxifying reactive intermediates in the Maillard reaction and catabolism of extensively browned proteins are also discussed, along with recent approaches for therapeutic modulation of advanced stages of the Maillard reaction.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Entomologia experimentalis et applicata 91 (1999), S. 403-412 
    ISSN: 1570-7458
    Keywords: aphid ; Diuraphis noxia ; Triticum aestivum ; endosymbiont ; insect-plant interactions ; phloem ; amino acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The feeding behavior of Diuraphis noxia Mordvilko (Homoptera: Aphididae) on susceptible hosts causes both ultrastructural and tissue level damage which may affect phloem composition. Genetic evidence suggests that endosymbiotic bacteria in most aphids overproduce limiting amino acids to benefit hosts but that D. noxia depends less on endosymbionts for these nutrients, possibly due to an enriched diet. To determine whether D. noxia feeding damage results in higher concentrations of essential amino acids, stylet exudates were analyzed from wheat (Triticum aestivum) damaged to different degrees. Comparison of samples from undamaged and damaged susceptible wheat revealed changes in amino acid composition and an increase in levels of essential amino acids, indicating a nutritionally enhanced ingesta. The changes in stylet exudates paralleled changes in leaf exudates, indicating that the effects are systemic. Feeding damage is not observed on a resistant wheat host, var. Halt, and leaf exudates from infested Halt did not show changes in amino acid composition. Mean relative growth of nymphs was significantly lower on Halt than on susceptible Arapahoe, indicating that Halt is a less suitable host. Both varieties show similar amino acid levels in non-infested samples, suggesting that D. noxia infestation does not enhance the phloem environment in Halt. This study provides evidence that aphid feeding can generate a nutritionally enhanced phloem diet.
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  • 3
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    Springer
    Entomologia experimentalis et applicata 58 (1991), S. 69-74 
    ISSN: 1570-7458
    Keywords: Rhopalosiphum padi ; antixenosis ; plant resistance ; Triticum aestivum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Description / Table of Contents: Zusammenfassung Die Antixenose gegenüberRhopalosiphum padi (L.) in den drei Weizensorten Timmo, Moghan 2 und Ommid, von denen die zwei letzteren Sorten aus dem Iran stammen, wurde unter Verwendung des systemischen Insektizids Pirimicarb gemessen. Jeweils zwei Pflanzen aus verschiedenen Sorten wurden als Paar verwendet (in allen Kombinationen der drei Sorten), pro Paar ein Topf mit Pirimicarb gegossen, und zwanzig Blattlaüse über Blattflächen von beiden Sorten gekäfigt. Ähnliche Versuche wurden auch ohne Insektizid ausgeführt. Beide Methoden zeigten deutliche Antixenose von Moghan 2 und Ommid in Vergleich mit Timmo. Die Insektizidmethode zeigte auch eine Bevorzugung von Moghan 2 gegenüber Ommid, ein Resultat, das mit der schon bekannten relativen Antibiose dieser zwei Sorten übereinstimmte, während sich ohne Insektizid kein solcher Unterschied erwies. Die statistische Analyse solcher Versuche mit einem Insektizid, die eine Modifikation der Berechnung des erwarteten Werts mit dem χ2 Test enthält, ist beschrieben.
    Notes: Abstract Antixenosis in three wheat varieties (Timmo, Moghan 2 and Ommid) toRhopalosiphum padi (L.) was measured by pairing plants of any two varieties with one plant of each pair treated with a soil drench of the systemic insecticide pirimicarb. Aphids were then allowed access to equivalent leaf areas from the two plants in a leaf cage. The results were compared with similar choice experiments without insecticide. By either technique, the two Iranian varieties (Moghan 2 and Ommid) showed antixenosis in comparison with Timmo. The statistical analysis of the data, using a heterogeneity χ2 test, is described.
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  • 4
    ISSN: 1570-7458
    Keywords: LepidopteraEphestia kuehniella ; α-amylase ; Triticum aestivum ; endosperm ; α-amylase inhibitors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Crude α-amylase preparations from seven Lepidoptera pests were susceptible to inhibition by salt-soluble proteins of bread wheat (Triticum aestivum L.) endosperm. Protein fractions that corresponded to tetrameric, dimeric, and monomeric wheat α-amylase inhibitors, were decreasingly effective against the insect α-amylase activity. To further confirm these results, purified inhibitors were tested against an α-amylase preparation fromEphestia kuehniella (Zeller). This preparation showed decreased activity when increasing amounts of an heterotetrameric inhibitor (reconstituted from its isolated subunits WTAI-CM2, -CM3 and -CM16) were assayed. Activity was only partially inhibited by homodimeric (WDAI-1, synonym 0.53; WDAI-2, synonym 0.19) and monomeric (WMAI-1, synonym 0.28) inhibitors.
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  • 5
    ISSN: 1570-7458
    Keywords: sieve element ; salivation ; aphid ; plant resistance ; wheat ; Sitobion fragariae ; Triticum aestivum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Extended sieve element salivation (E1 waveform in the electrical penetration graph) is a characteristic activity during early sieve element punctures, particularly in resistant plants. In order to explore a chemically-mediated mechanism of resistance associated with sieve element salivation, we compared the pattern of feeding behaviour of the aphid, Sitobion fragariae (Walker), on two cultivars of the wheat Triticum aestivum L., with different concentrations of hydroxamic acids (Hx). During 24 h of electronic monitoring, aphids dedicated over 50% of the total time to phloem ingestion from the sieve elements. Total time allocated to E1 in the experiment, time to first E1 within the experiment, time allocated to E1 before a sustained phloem ingestion (E2) and the contribution of sieve element salivation to the phloem phase (E1/[E1+E2]) were significantly higher in the high-Hx cultivar. The increased salivation in plants with higher contents of Hx suggests the existence, at least in this system, of a chemically-mediated sieve element constraint.
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  • 6
    ISSN: 1572-8862
    Keywords: Palladium ; carbene ; oxidation ; phosphonate ; carboxylate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Thermolysis of tetranuclear palladium clusters Pd4(μ-Q)4 Pd4(μ-Q)4(μ-O2CR)4 (Q=CPh2 or CO;R=Me, CMe3, Ph, CH2Cl or CF3) has been found to involve innersphere oxidation of carbene or carbonyl ligands during which an oxygen atom transfer occurs from the carboxylate group to the carbene or carbonyl ligand. The thermolysis of the carbonyl clusters gives rise to the products of CO2 insertion into the C–H bond of benzene or toluene used as solvents forming benzoic acid from benzene and a mixture of phenylacetic and toluic acids from toluene. The reaction of [Pd(OAc)2(PPh3)]2 with HCO2H includes the transfer of an O atom from formate ligand to the P atom and cleavage of the P-Ph bond accompanied by transfer of the Ph group from PPh3 ligand to the palladium atom. The structure of the complex formed, [Pd(μ-O2PPh2)(C6H5)(PPh3)]2, has been resolved by X-ray analysis.
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  • 7
    ISSN: 1572-8900
    Keywords: Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene (ABS) ; ABS/polycarbonate blend
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The thermal oxidative stability of various ABS/PC compounds was studied by means of the chemiluminescence technique. Similarly to pure ABS, Irganox 1076 and Irganox MD 1024 perform as moderate antioxidants in ABS/PC and (ABS/PC + lubricant) blends. Neither Tinuvin 144, Irgaphos 168, nor their mixture affects the durability of the ABS/PC blend. At the same time, (Irgaphos 168 + Tinuvin 144) in combination with Irganoxes was found to provide a noticeable enhancement in durability to the (ABS/PC + lubricant) system. Titanium dioxide pigments by themselves have only a slight influence on the oxidative stability of the ABS/PC blend. Durability of the (ABS/PC + pigment) and (ABS/PC + lubricant) systems was found to be the same and the overall protective effect of Irganox 1076 was similar in both the (ABS/PC + lubricant) and the (ABS/PC + lubricant + pigment) systems. Certain modifiers significantly improve the durability of the ABS/PC compounds, although their function may differ in the systems with and without pigments.
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  • 8
    ISSN: 1572-8900
    Keywords: Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene (ABS)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of lubricants, UV stabilizers, antioxidants, and metal deactivators on the resistance of ABS to thermal oxidation was studied by means of the chemiluminescence technique. Neither of the additives seems to affect significantly the induction period of oxidation. At the same time, the influence of various additives on the oxidation rate constant is remarkably different: the introduction of lubricants and UV stabilizers increases its value, while antioxidants and metal deactivators have the opposite effect. For the particular systems studied durability is decreased in samples containing the lubricant and UV stabilizers and increased in samples stabilized with the antioxidant and metal deactivator.
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  • 9
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    Journal of applied electrochemistry 27 (1997), S. 1275-1282 
    ISSN: 1572-8838
    Keywords: Carbon monoxide ; Pt-Ru/C catalyst ; Tafel slopes ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract CO electrooxidation on a Pt–Ru/C catalyst was investigated in sulphuric acid electrolyte. The physico-chemical properties of the Pt–Ru/C catalyst were studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The influence of temperature, CO partial pressure and proton concentration on the electrochemical oxidation rate was investigated by steady-state galvanostatic polarization measurements. The apparent activation energy decreased from 70 to 30kJmol−1 as the overpotential increased from 0.5 to 0.9V vs NHE. The reaction order with respect to carbon monoxide increased, passing from 0.4 to 1, with the increase of the overpotential from 0.5 to 0.7V vs NHE; a reaction order close to −1 with respect to the protonic concentration was observed, irrespective of the potential. Tafel slopes of about 136mVdec−1 were determined for oxidation of CO and CO/N2 mixtures.
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  • 10
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    Journal of applied electrochemistry 28 (1998), S. 607-612 
    ISSN: 1572-8838
    Keywords: SnO2 anodes ; doping ; high overvoltage anodes ; surface analysis ; oxidation ; water treatment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Doped tin dioxide electrodes have been prepared by a standard spray pyrolysis technique. The electrochemical behaviour of these electrodes has been investigated by cyclic voltammetry in sulphuric acid using the Fe2+/Fe3+ redox couple system as test reaction. Oxygen evolution has been used to study the stability of doped SnO2 electrodes. The SnO2 electrodes doped with antimony and platinum exhibit the highest stability. XPS analysis shows that the oxidation state of Sn, Sb and Pt are +4, +3 and +2, respectively, the probable species being SnO2, Sb2O3 and PtO.
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  • 11
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    Journal of inorganic and organometallic polymers and materials 1 (1991), S. 389-395 
    ISSN: 1572-8870
    Keywords: Poly(organophosphazenes) ; cyclophosphazenes ; Rose Bengal ; photosensitization ; singlet oxygen ; oxidation ; heterogeneous phase photosensitizer ; 1,3-diphenyl-isobenzofuran
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this paper we report the synthesis and the characterization of cyclo- and polyphosphazenes supporting Rose Bengal. These substrates are suitable for the photosensitized generation of singlet oxygen, both in homogeneous and in heterogeneous phase. The efficiency of1O2 production has been measured in homogeneous solution using, as photosensitizer, the cyclophosphazene-bound Rose Bengal and considering, as testing reaction, the oxidation of 1,3-diphenylisobenzofuran; it was found comparable to that of free Rose Bengal in the same experimental conditions.
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  • 12
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    Journal of applied electrochemistry 30 (2000), S. 727-731 
    ISSN: 1572-8838
    Keywords: electrosynthesis ; oxidation ; lignin ; vanillin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Electrochemical oxidative degradation of Kraft lignin was investigated in batch and flow cells on Pt, Au, Ni, Cu, DSA–O2 and PbO2 anodes. Production of vanillin was evaluated by means of formal kinetic analyses. Conversion and chemical yields were found to be dependent mainly on the applied current density, that is on the partial pressure of oxygen at the interface, while the nature of the electrode influenced the reaction rates.
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  • 13
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    Journal of chemical crystallography 28 (1998), S. 119-123 
    ISSN: 1572-8854
    Keywords: Azetidine ; azetine ; ring opening ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract 1-Acetyl-3-bromo-3-phenylazetidine (1), C11H12BrNO, has been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. It crystallizes in the space group P2 1/c with a = 8.633(1), b = 7.461(1), c = 17.204(1) Å, β = 98.403(7)°, V = 1096.2(2) Å3, Z = 4, D calc = 1.540 g cm−3. The azetidine ring is nearly planar since the four atoms are within ±0.039(5) Å of the mean square plane calculated for the heterocycle. The attempt to obtain a highly strained 2-azetine derivative from the above compound gave, surprisingly, 1-phenyl-2-(N-acetyl-N-formyl)-aminoethanone (2), C11H11NO3. This compound has been also characterized by spectroscopic methods and single crystal X-ray analysis. It crystallizes in the space group P212121, with a = 5.4719(3), b = 8.3205(6), c = 23.298(3) Å, V = 1060.7(2) Å3, Z = 4, D calc = 1.286 g cm−3. The aminoethanone residue is in a near planar conformation where the torsion angles are 7(2)° for N–C–C–=O and −173(2)° for N–C–C–C(Ph).
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  • 14
    ISSN: 1572-8870
    Keywords: Polyorganosiloxane ; cobalt(II)phthalocyanine ; polymeric catalyst ; oxidation ; 3-methylindole ; polymer conformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Two kinds of cobalt(II)phthalocyanines covalently bound to polyorganosiloxane (POS) were prepared to be applied as catalysts for the oxidation of 3-methylindole in organic solvents. The catalytic activity of the POS whose carboxyl residues were methyl-esterified was high compared with that of the POS which has carboxyl residues. The former polymeric atalyst exhibited higher catalytic activity than monomolecular phthalocyanine, indicating an appearance of effects of polymer chains. The factors which influence the catalytic oxidation, e.g., polymer conformations, basicity of solvents, and equilibrium involving phthalocyanine monomer and the dimer, are discussed. It has become apparent that polymer conformation influences catalytic activity and that the catalytic activity of the POS, whose main chains are mobile, is high.
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  • 15
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    Journal of polymers and the environment 3 (1995), S. 199-203 
    ISSN: 1572-8900
    Keywords: Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The thermal oxidative stability of various formulations based on emulsion-grade ABS was studied by the chemiluminescence technique. Emulsion products were found to be essentially less stable than ionic mass polymerization resins. Among the antioxidants studied, Santonox R is clearly more efficient than Irganox 1076 and Irganox 3114, and its superiority is reflected primarily in improved induction period values. The introduction of Tinuvin 770 and Tinuvin 328 UV stabilizers into emulsion resins does not change the durability of the products. In mixtures where both Irganox 1076 and UV stabilizers are present, a certain antagonistic effect was noted at high UV stabilizer concentrations.
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  • 16
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    Journal of solution chemistry 20 (1991), S. 1079-1092 
    ISSN: 1572-8927
    Keywords: Fe(II) ; oxidation ; H2O2 ; ionic strength ; NaCl ; NaClO4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of Fe(II) with H2O2 has been measured in NaCl and NaClO4 solutions as a function of pH, temperature T (K) and ionic strength (M, mol-L−1). The rate constants, k (M−1-sec−1), d[Fe(II)]/DT=-k[Fe(II)][2O2] at pH=6.5 have been fitted to equations of the form log k = log k0+ AI 1/2+BI+CI 1/2/T Where log k0=15.53-3425/T in water; A=−2.3, −1.35; B=0.334, 0.180; and C=391, 235, respectively, for NaCl (σ=0.09) and NaClO4 (σ =0.08). Measurements made in NaCl solutions with added anions yield rates in the order B(OH) 4 − 〉HCO 3 − 〉ClO 4 − 〉Cl−〉NO 3 − 〉SO 4 2− and are attributed to the relative strength of the interactions of Fe2+ or FeOH+ with these anions. The FeB(OH) 4 + species is more reactive while the FeCO 3 0 , FeCl+, FeNO 3 + and FeSO 4 0 species are less reactive than the FeOH+ ion pair. The general trend is similar to our earlier studies of the oxidation of Fe(II) with O2 except for B(OH) 4 − . The effect of pH on the logk was found to be a quadratic function of the concentration of H+ or OH− from pH=4 to 8. These results have been attributed to the different rate constants for Fe2+ (k0) and FeOH+ (k1) which are related to the measured k by, k=k0αFe + k1αFeOH, where αi is the molar fraction of species i. The rates increase due to the greater reactivity of FeOH+ compared to Fe2+. k0 is independent of composition and ionic strength but k1 is a function of ionic strength and composition due to the interactions of FeOH+ with various anions.
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  • 17
    ISSN: 1572-8757
    Keywords: porous carbons ; activation ; oxidation ; surface oxygen groups ; LTPD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A styrene/divinylbenzene copolymer has been used as precursor for making porous carbons with bimodal pore size distributions (i.e., with both microporosity and mesoporosity). Pretreatment of the as-received copolymer by mild oxidation in air, significantly increased the carbon yield after carbonization. Reactivity studies of the polymer-based chars to CO2 clearly show the influences of some important factors such as carbonization temperature, heating rate, soak time on char reactivities. Bimodal porous carbons were prepared by carbonization of the preoxidized styrene/divinylbenzene copolymer in N2, followed by activation in CO2 at different temperatures to different levels of burnoff. The pore structures of the porous carbons produced have been characterized by various techniques such as gas adsorption and mercury porosimetry. The surfaces of the porous carbons produced, and a commercial carbon adsorbent, have been modified with HNO3 and H2O2 treatment at various conditions. Characterization of the surface oxygen functionality, both quantitatively and qualitatively, has been achieved using techniques such as Linear Temperature Programed Desorption (LTPD) and selective neutralization of bases.
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  • 18
    ISSN: 1572-8765
    Keywords: carbonado ; diamond ; 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 oxidation of carbonado type synthesized polycrystalline diamonds produced from graphite together with catalytic Ni-Mo alloy doped with TiB2 and BNcub was investigated. It was found that the addition of these boron compounds increases the oxidation resistance of the carbonado type synthesized polycrystalline diamonds. The oxidation mechanism acting on the carbonado type synthesized polycrystalline diamonds and the role of boron compounds in increasing the resistance to the oxygen reaction are discussed.
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  • 19
    ISSN: 1572-879X
    Keywords: Silica ; oxidation ; methane ; carbon monoxide ; carbon dioxide ; labelled reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of carbon monoxide to carbon dioxide is shown to be catalyzed at 850 K or above over almost all lattice oxygen atoms on the surface of silica prepared by the sol-gel method from ethyl orthosilicate under conditions which yield high selectivity to carbon dioxide in the oxidation of methane.
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  • 20
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    Catalysis letters 16 (1992), S. 149-158 
    ISSN: 1572-879X
    Keywords: Silver ; oxidation ; cyclohexenes ; branched chain olefins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of some cyclic and branched chain olefins over a silver catalyst effective for the conversion of ethylene to ethylene oxide has been investigated in a steady state flow system. The reaction of cyclohexene produces benzene and that of both 1-methylcyclohexene and 4-methylcyclohexene yields toluene. The selectivity to aromatics exceeds 20% for fractional conversions below 0.2, but it can be improved to almost 50% by inclusion of an optimum quantity of dichloroethane in the feed. Styrene is oxidised more slowly than the cyclohexenes and only carbon dioxide and water are produced. The oxidation of 3,3-dimethyl-1-butene and 3-methyl-1-butene occurs much faster than that of the cyclic molecules and some of the corresponding epoxides are produced. The selectivity with the dimethyl-butene is 9–13% for conversions to 0.2. The methylbutene requires a higher temperature for reaction and the epoxide yield is lower. Factors influencing reactivity and product distribution are discussed.
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  • 21
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
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  • 22
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    Catalysis letters 13 (1992), S. 9-19 
    ISSN: 1572-879X
    Keywords: Vanadia ; titania ; silica ; Raman ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of V2O5/TiO2/SiO2 catalysts were structurally investigated byin situ Raman spectroscopy and chemically probed by methanol oxidation in order to determine the molecular structure-reactivity relationships of the V2O5/TiO2/SiO2 catalysts. Only surface TiO x species are present on the 3% TiO2/SiO2 catalysts, and the surface TiO x species as well as bulk TiO2 (anatase) particles coexist on the 40% TiO2/SiO2 catalyst. The deposition of 1–3% vanadium oxide onto 3% TiO2/SiO2 and 4% vanadium oxide onto 40% TiO2/SiO2 forms only a surface vanadium oxide phase.In situ Raman studies reveal that the surface vanadium oxide species preferentially exist on the titania sites of the TiO2/SiO2 system. The interaction between the surface vanadia and the surface titania overlayer on SiO2 increases the methanol oxidation reactivity by two orders of magnitude relative to V2O5/SiO2. In the presence of bulk TiO2 (anatase) particles on the SiO7 support, the reactivity of the surface vanadia further increases by an order magnitude relative to the catalysts containing only surface titania, and is close to that of surface vanadia on bulk TiO2. This suggests that the surface VO x -TiO2 (bulk) interactions results in a more active site than the surface VO x -TiO x -SiO2 interactions. In addition, the V2O5/TiO2/SiO2 catalysts exhibit high selectivity towards HCHO because redox sites are predominant on the surface of these catalysts with essentially no acid site present.
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  • 23
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    Catalysis letters 13 (1992), S. 341-347 
    ISSN: 1572-879X
    Keywords: Methane ; oxidation ; oxidative coupling ; hydroformylation ; propanal ; catalysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract High yield synthesis of propanal from methane and air can be obtained in a single pass at atmospheric pressure. Three catalytic processes are combined to give 13% yield of propanal based on total methane input. Ethene is made from the oxidative coupling reaction and carbon monoxide and hydrogen is generated from partial oxygenation of methane. These gases are combined and passed to a hydroformylation catalyst to give liquid propanal. The unreacted methane is inert in the hydroformylation stage, while oxygen deactivates the catalyst readily. The results imply that propanal can be obtained, in good yield, from methane and air provided that total oxygen conversion is achieved. The yield of propanal from the three combined processes can be substantially higher than that of ethene from the oxidative coupling reaction. Thus, higher yields of a condensible and oxygenated product are obtained.
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  • 24
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    Catalysis letters 37 (1996), S. 213-216 
    ISSN: 1572-879X
    Keywords: titanium silicalites ; oxidation ; amines ; hydrogen peroxide
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    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.
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  • 25
    ISSN: 1572-879X
    Keywords: Methane ; formaldehyde ; oxidation ; vanadium oxide ; silica
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Methane oxidation to formaldehyde was studied over a vanadium oxide catalyst supported on silica at 630 °C using the technique known as temporal analysis of products with sequential pulsing of methane and oxygen. This work shows that methane interacts very weakly and oxygen very strongly with the catalyst surface and it is concluded that the initial activation of methane involves an adsorbed oxygen species. Methyl radicals formed in the first step subsequently extract lattice oxygen to yield formaldehyde.
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  • 26
    ISSN: 1572-879X
    Keywords: Metallonitroporphines ; oxidation ; isobutane ; propane
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Introducing nitro groups into themeso-positions of a metalloporphyrin converts a catalytically inactive complex into a highly active catalyst for the oxidation of alkanes with molecular oxygen. The degree of nitration correlates with both the Fe(III)/Fe(II) reduction potential and the catalytic activity.
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  • 27
    ISSN: 1572-879X
    Keywords: oxidation ; cyclohexene ; polyoxometalate-intercalated hydrotalcite
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    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.
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  • 28
    ISSN: 1572-879X
    Keywords: palladium metal ; oxidation ; toxic organics
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    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.
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  • 29
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    Catalysis letters 34 (1995), S. 31-40 
    ISSN: 1572-879X
    Keywords: palladium ; PdO ; alumina ; methane ; oxidation ; carbon ; XPS ; ellipsometry ; structure sensitivity
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Samples of palladium supported onγ-alumina and a palladium foil were used as catalysts for methane oxidation at 550° C. The samples were quenched quickly in the reaction chamber to room temperature in flowing Ar and then transferred in vacuo for XPS analysis. Structure sensitivity was manifest from an increase in PdO stability and a decrease in carbon deposition relative to Pd with increasing particle size. The results were compared with recent ellipsometric data.
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  • 30
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    Catalysis letters 52 (1998), S. 25-29 
    ISSN: 1572-879X
    Keywords: metallosilicate ; mesoporous ; MCM-41 ; Mo-MCM-41 ; catalysis ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Mo-incorporated MCM-41 has been prepared by direct hydrothermal synthesis. XRD and N2-adsorption measurements showed the characteristics of MCM-41. IR, FT-Raman and UV-VIS DR spectroscopic analyses gave the evidences for the incorporation of Mo in the framework of MCM-41. They are found to be stable and active for cyclohexanol and cyclohexane oxidation reactions with H2O2 as oxidant. Activity of this system has been compared with that of Ti-MCM-41 and molybdena impregnated on pure siliceous MCM-41.
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  • 31
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; calcium-based catalysts ; tetrachloromethane
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of propane has been investigated in the presence and absence of tetrachloromethane (TCM) on calcium hydroxyapatite (CaHAp), Ca3(PO4)2, CaSO4 and CaO at 723 K. In the absence of TCM, the conversion of C3H8 on CaHAp was 7.7–9.2% during 6 h on-stream while that on Ca3(PO4)2, CaSO4 and CaO was 0.6, 0 and 0.2–0.4%, respectively. The principal products on all catalysts in the absence of TCM were CO and CO2 with small selectivities to C3H6 and C2H4 (both 5–6%) observed on CaHAp. Upon addition of TCM, the selectivity to C3H6 on all catalysts and the conversion of C3H8 on CaSO4 increased while, with increasing time-on-stream, the changes in the conversion and selectivity were dependent upon the nature of the catalysts. XPS and XRD analyses provide evidence for the presence of chlorine in the surface and/or bulk of three of the catalysts, suggesting that chlorinated species on the solids play a role in the selectivity enhancement, but the absence of chlorine from the sulphate demonstrates the dissimilarities of the catalysts in their abilities to sorb and decompose TCM.
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  • 32
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; strontium hydroxyapatite ; lead hydroxyapatite ; tetrachloromethane
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of methane has been investigated on lead hydroxyapatite (PbHAp), strontium hydroxyapatite (SrHAp) and their binary mixtures at 873 K. PbHAp showed no activity for the oxidation of methane, while SrHAp produced carbon monoxide selectively at 2–4% conversion. On binary mixtures of the hydroxyapatites the conversion of methane and the selectivity to C2 compounds reached values higher than those of the separate constituents of the mixture. With tetrachloromethane in the feed stream a similar synergistic effect was observed with conversions of methane and selectivities to CH3Cl higher on the binary mixtures than those on either SrHAp or PbHAp. The strontium-containing hydroxyapatite appears to play a crucial role in the activation of methane, while the presence of the lead-containing analogue is apparently required for the minimization of undesirable processes involving methyl radicals.
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  • 33
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    Catalysis letters 9 (1991), S. 133-143 
    ISSN: 1572-879X
    Keywords: Norbornene ; oxidation ; silver ; norbornene epoxide ; 3-cyclohexene-1-carboxyaldehyde
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The continuous oxidation of norbornene (C7H10) by molecular oxygen over a silver catalyst at 500–573 K has been investigated. In contrast to that observed during the temperature programmed reaction of norbornene and oxygen adsorbed on Ag(110) no norbornene epoxide is formed. Instead benzene is the sole partial oxidation product. A stable selectivity of 20 to 25% with fractional conversions up to 0.8 at 573 K could be obtained by inclusion of 15 to 30 ppm dichloroethane in the feed. Separate experiments withexo-norbornene epoxide showed that in the absence of oxygen it was almost completely isomerised to 3-cyclohexene-1-carboxyaldehyde with production of lesser amounts of norcamphor and norbornene. With oxygen present carbon dioxide and small amounts of benzene were also produced. It is concluded that norbornene epoxide cannot be a gas phase intermediate in the production of benzene from norbornene.
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  • 34
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    Catalysis letters 15 (1992), S. 401-404 
    ISSN: 1572-879X
    Keywords: Acrylic acid ; oxidation ; mixed oxides ; acrolein
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Catalytic oxidation of acrolein to acrylic acid has been studied and the optimum composition of the multicomponent catalyst Mo a V b Cu c Fe d O x has been found. The reaction kinetics has been measured.
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  • 35
    ISSN: 1572-879X
    Keywords: coke ; zeolites ; catalyst regeneration ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract SAPO-18, which has a microporous framework structure related to, but crystallographically distinct from, that of the solid acid catalyst SAPO-34, was synthesized hydrothermally from a silicoaluminophosphate gel containing N,N-diisopropylethylamine as a structuredirecting template. Although both materials have similar Si/(Si + Al + P) ratios, the content of Brønsted acid sites in SAPO-18 is considerably less than that in SAPO-34. As catalysts for methanol conversion to light olefins, SAPO-18 and SAPO-34 have closely similar initial activity and selectivity, but the lifetime of SAPO-18 is distinctly superior to that of SAPO-34.
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  • 36
    ISSN: 1572-879X
    Keywords: fluorination ; alumina ; platinum catalysts ; oxidation ; oxidation of benzene
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    Notes: Abstract Platinum supported on fluorinated alumina is more active for the total oxidation of benzene than is the catalyst with the same Pt loading supported on hydrophilic unfluorinated alumina. The Pt-F/alumina catalyst contains well-dispersed small Pt particles, in contrast to Pt/alumina. The high dispersion is a consequence of a strong metal-support interaction.
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  • 37
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    Catalysis letters 7 (1990), S. 241-251 
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; iron based catalysts ; Fe ; Co ; Ru catalysts ; fixed bed reactors ; fluidized bed reactors ; sulfur poisoning ; oxidation ; coke fouling
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Because of the decreased profitability of making synthetic fuels, Sasol intends expanding its production of the higher valued chemicals, in particular waxes and olefins. The advantages and disadvantages of using Fe, Co and Ru catalysts are discussed from the point of view of costs, availability, product selectivity, activity and sensitivity to poisons. The loss of activity and selectivity of iron based catalysts in both fixed and fluidized bed reactors is discussed. The main contributing factors are sulfur poisoning, oxidation and coke fouling. In fixed bed reactors sulfur poisoning and “coke” laydown deactivates the front end of the bed while hydrothermal sintering/oxidation deactivates the back end. In fluidized beds the deposition of large amounts of Boudouard carbon doesnot markedly lower the activity. The smaller catalyst particles end up consisting of small iron carbide entities embedded in a matrix of carbon. The larger catalyst particles consist of cores of inert magnetite surrounded by the carbide/carbon matrix. FT reactor development at Sasol is briefly reviewed.
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  • 38
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    Catalysis surveys from Japan 3 (1999), S. 55-60 
    ISSN: 1572-8803
    Keywords: acetic acid ; oxidation ; Pd ; heteropoly acid ; ethylene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new process for acetic acid production by direct oxidation of ethylene which was established and commercialized is described. The catalyst system consisting of Pd and heteropoly acid exhibits excellent activity and selectivity. The addition of Se or Te to the catalyst system is effective to suppress the formation of carbon dioxide. This new process is applicable to a plant of a wide range of size corresponding to the local demand. Because this new process produces little waste water, it is very friendly to the environment.
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  • 39
    ISSN: 1572-879X
    Keywords: oxidation ; reduction of palladium catalysts ; chlorine effects
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Pd–chloride precursor salt was used to prepare Pd/Al2O3 catalysts. TPSR measurements showed three distinct reactions for the oxidation of propane on palladium surface under excess of hydrocarbon: complete oxidation, steam reforming and propane hydrogenolysis. Propane oxidation on palladium catalysts was related to the Pd2+ sites observed on Pd/Al2O3 through infrared of adsorbed carbon monoxide. In fresh catalysts reduced by H2, the IR spectra showed the linear and bridge adsorbed CO species on the Pd0 surface. After propane reaction, a new band at 2130 cm-1 related to CO adsorption on Pd2+ species was noted. Carbon monoxide species adsorbed on Pd0 were also observed in all samples after reaction. Our results suggest surface ratios of Pd0/PdO during the propane oxidation. On the other hand, time on stream conversions of the complete oxidation of propane were affected by either the water generated during the reaction or added as a reactant at 10 vol%. The water generated by the reaction helped to eliminate chlorine residues in the form of oxychloride species leading to an increasing of the activity. However, the presence of water into the reaction mixture caused a strong decreasing of the activity. The inhibition mechanism of propane oxidation in the presence of water consisted in the dissociative adsorption of water on palladium sites with the possible formation of palladium hydroxide (Pd–OH) at the surface, diminishing the number of active surface sites. Dynamic fluctuations into the reaction conditions supported the idea that a pseudo‐equilibrium adsorption–desorption of water was reached. After water removal or increasing in the reaction temperature the equilibrium was shifted to the direction of OH–Pd decomposition. This behavior suggests that the inhibitory effect of water is a reversible phenomenon, being a function of the amount of water and the reaction temperature.
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  • 40
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    Cellulose 5 (1998), S. 153-164 
    ISSN: 1572-882X
    Keywords: cellulose ; TEMPO ; polyglucuronic acid ; degree of polymerization ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Various cellulose samples were oxidized by 2,2,6,6,-tetramethylpipelidine-1-oxyl radical (TEMPO)-NaBr-NaClO systems, and the effects of oxidation conditions on chemical structures and degrees of polymerization of the products obtained were studied. In the case of regenerated and mercerized celluloses, almost all C6 primary alcohol groups were selectively oxidized to carboxyl groups, and water-soluble polyglucuronic acid (cellouronic acid) sodium salts were obtained almost quantitatively; the degrees of polymerization were influenced greatly by the amount of TEMPO added, and the oxidation time and temperatures. Cellouronic acids prepared from mercerized linter and kraft pulps had size exclusion chromatograms with two separate peaks due to higher and lower molecular weight fractions. On the other hand, only small amounts of carboxyl groups were introduced into native cellulose samples. Since polyglucuronic acids prepared from cellulose by the TEMPO–NaBr– NaClO systems regularly consist of the glucuronic acid repeating unit, differing from the conventional water-soluble cellulose derivatives, they may open new fields of cellulose utilization.
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  • 41
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    Catalysis surveys from Japan 2 (1998), S. 121-132 
    ISSN: 1572-8803
    Keywords: zeolite ; metallosilicate ; atom-planting ; modification ; catalysis ; acidity ; shape-selective alkylation ; oxidation ; hydrogen peroxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Atom-planting, a useful method to prepare some metallosilicates having zeolitic structure, was proposed. By treatment of highly siliceous zeolite with metal chloride vapor at selected temperature, metal cation could be introduced into the defect sites (hydroxyl nests) of zeolite framework. By the atom-planting method, some metallosilicates which are difficult to be synthesized by hydrothermal synthesis could be prepared. The vapor phase shape-selective alkylation of ethylbenzene with ethanol, and the liquid phase selective oxidation with hydrogen peroxide on the metallosilicates prepared by atom-planting method were reviewed.
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  • 42
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; aliphatic hydrocarbons ; zeolite ; recycle reactor
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Conversion of methane in high yields to C4+ nonaromatic hydrocarbons was demonstrated in a recycle system. The principal components of the recycle system included an oxidative coupling reactor with a Mn/Na2WO4/SiO2 catalyst at 800°C for conversion of methane to ethylene, and a reactor with an H-ZSM-5 zeolite at 275°C for subsequent conversion of ethylene to higher hydrocarbons. Total yields of C4+ products were in the range of 60–80%, and yields of C4+ nonaromatic hydrocarbons were in the range of 50–60%.
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  • 43
    ISSN: 1572-9028
    Keywords: oxidation ; oxyacetoxylation ; alloy ; palladium ; bismuth ; benzylacetate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Benzylacetate synthesis from toluene, acetic acid and oxygen on Pd–Bi binary catalyst was studied in the liquid phase. By incorporation of Bi with Pd, both the activity and selectivity were improved. Especially better stability was obtained with the catalyst having Pd/Bi = 3. Deactivation of the catalyst was investigated in detail by XRD, XPS, TEM, elemental analysis, EPMA and so on. Comparing the used catalyst with the fresh one, it was indicated that the main cause of deactivation was the dissolution of Pd into the reaction mixture from the most outer surface of the catalyst. By adopting proper reaction conditions to prevent the Pd dissolution, the catalyst having Pd/Bi = 3 was suggested to be used as an industrial catalyst.
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  • 44
    ISSN: 1572-9028
    Keywords: nitric oxide ; ammonia ; oxidation ; X-ray photoelectron spectroscopy ; scanning tunnelling microscopy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The dissociative chemisorption of nitric oxide at Cu(110) has been shown to result in rapid ordering of oxygen adatoms as (2×1)O chains oriented along the 〈100〉 direction while the associated nitrogen adatoms are mainly disordered at 295 K. Surface diffusion of the N adatoms, following bond cleavage, is activated and ordering of the (2×3)N strings occurs on heating to 430 K. A number of distinct reaction pathways have been isolated during the oxidation of ammonia resulting in the formation of either chemisorbed imide or nitrogen adatoms. The latter depending on temperature, may exhibit a (2×3)N, a (3×3)N or both structures may exist simultaneously. The concentration of nitrogen in the complete (2×3)N structure has been determined to be 6.6×1014 cm-2, with only a 25% decrease in nitrogen concentration leading to the transformation to the (3×3)N structure. The oxygen atoms at a Cu(110)–O overlayer, and present at the ends of the (2×1) strings terminating in steps, show specific reactivity when exposed to ammonia at 375 K resulting in the “decoration” of the steps with imide species while the oxygens within the (2×1) strings remain unreactive.
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  • 45
    ISSN: 1572-879X
    Keywords: alkylbenzene ; toluene ; ethylbenzene ; xylene ; mesitylene ; p‐ethyltoluene ; cumene ; p‐cymene ; oxidation ; palladium ; 1,10‐phenanthroline
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Only the side‐chain oxidation of alkylbenzenes (R–C6H3–R′–R″ R=H, Me, Et, Pri R′=H, Me; and R″=H, Me) by oxygen (35–50 atm, 200)C° is promoted in the presence of [Pd(phen)(OAc)2].
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  • 46
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    Entomologia experimentalis et applicata 59 (1991), S. 79-85 
    ISSN: 1570-7458
    Keywords: Wheat ; Triticum aestivum ; cereals ; Rhopalosiphum padi ; Aphididae ; barley yellow dwarf virus ; hydroxamic acids ; DIMBOA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract 2,4-Dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA), a hydroxamic acid (Hx) occurring in wheat, was shown to deter feeding by the aphid Rhopalosiphum padi (L.), and to reduce BYDV transmission to the plant. Dual choice tests with wheat leaves showed the preferential settlement of aphids on leaves with lower levels of DIMBOA. Electric monitoring of aphid feeding behaviour showed that in seedlings with higher DIMBOA levels fewer aphids reached the phloem and they needed longer times to contact a phloem vessel than in those with lower levels. When aphids carrying BYDV were allowed to feed on wheat cultivars with different DIMBOA levels, fewer plants were infected with BYDV in the higher DIMBOA cultivars than in the lower ones. Preliminary field experiments showed a tendency for wheat cultivars with higher Hx levels to be more tolerant to infection by BYDV than lower Hx level ones.
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  • 47
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    Catalysis surveys from Japan 2 (1998), S. 31-44 
    ISSN: 1572-8803
    Keywords: porous heteropoly compounds ; Pt-promoted heteropoly compounds ; shape selectivity ; water-tolerant catalyst ; hydrogenation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper attempts to review recent works on catalysis of porous heteropoly compounds. The salts of heteropolyacids having Keggin structure with large cations like Cs+ are porous materials. For Cs hydrogen salts, the pore width can be controlled by the Cs content. Cs2.5H0.5PW12O40 has the largest amount of protons on the surface among the acidic Cs salts and possesses pores with bimodal distribution in the micro and meso region. Efficient performances were demonstrated for acid-catalyzed reactions such as skeletal isomerization of η-butane in solid-gas system, alkylation and acylation in solid-liquid system, and hydrolysis and hydration in solid-water system. A microporous salt, Cs2.2H0.8PW12O40, exhibited reactant shape selectivity towards direct decomposition of esters. Furthermore, an ultramicroporous bifunctional catalyst, Pt–Cs2.1H0.9PW12O40 of which the pore width is around 5 Å, exhibits reactant shape selectivity for hydrogenation of alkenes and oxidation of hydrocarbons, and product shape selectivity for skeletal isomerization of η-butane.
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  • 48
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    Topics in catalysis 11-12 (2000), S. 359-367 
    ISSN: 1572-9028
    Keywords: zeozyme ; encapsulated complexes ; copper acetate ; copper dimers ; enzyme mimic ; EPR of copper ; tyrosinase ; oxidation ; oxygenase ; tyrosine oxidation ; phenol oxidation ; hydroxylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxygenase mimicking activity of copper acetate dimers in the regioselective ortho-hydroxylation of L-tyrosine to L-dopa is enhanced on encapsulation in zeolite Y. The structure and magnetic properties of the catalytic active site were characterized by EPR spectroscopy. The spectra of this “zeozyme” reveal the presence of (1) copper acetate dimers in the supercages and (2) isolated Cu(II) ions in the sodalite cages of the zeolite. There are significant differences in the EPR spectra of the “neat” and encapsulated complexes: on encapsulation in zeolite, the Cu–Cu exchange coupling constant, −, increases to 310 from 259 cm−1 for the “neat” complex (i.e., by about 19.7%). Simultaneously the Cu–Cu separation in the dimer, estimated indirectly from the exchange coupling constant, shortens to 2.40 Å in the encapsulated state from 2.64 Å in the “neat” complex. There is, hence, a relatively greater overlap of the metal orbitals of the dimer copper atoms inside the restricted confines of the zeolite cages. The consequent, enhanced, trans axial lability of the phenolate and dioxygen ligands promotes the catalytic oxygenase activity of copper acetate dimers on encapsulation in zeolites. A causal relationship between changes in the structural features of an active site on encapsulation in the zeolite and the corresponding catalytic activity has, thus, been established.
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  • 49
    ISSN: 1572-879X
    Keywords: Propane ; butane ; alkane ; oxidation ; dehydrogenation ; vanadates ; cation reduction potential ; oxide structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidative dehydrogenation of butane over a series of orthovanadates of cations of different reduction potentials showed a correlation that the selectivity for dehydrogenation decreased with increasing ease of reduction of the cation. The highest selectivity was observed on Mg orthovanadate. Mg pyrovanadate was nonselective for butane oxidation, but was as selective as Mg orthovanadate in propane oxidation. These results were interpreted by the different structures of the two Mg vanadates.
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  • 50
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    Catalysis letters 16 (1992), S. 217-221 
    ISSN: 1572-879X
    Keywords: Methane ; ethane ; methanol ; ethanol ; ozone ; oxygen atom ; oxidation ; sensitization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction of O2, O3, and CH4 or C2H6 of 7.76, 0.24 and 92% of the hydrocarbon respectively (residence time of 8.8 min) at 1 atm, and 400 °C for CH4 and 300 °C for C2H6 gave CO, CO2, H2O, CH2O and CH3OH from CH4 and in addition CH4, C2H4, CH3CHO and C2H5OH from C2H6. No reaction occurred when O3 was absent indicating that the partial oxidation was sensitized (initiated) by the oxygen atoms formed by the decomposition of ozone.
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  • 51
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; platinum ; palladium ; sulfur dioxide ; alumina ; zirconia ; activity ; acidity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated γ-alumina or zirconia compared to γ-alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/γ-alumina, Pt/zirconia, Pd/γ-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/γ-alumina, and Pd/zirconia is less active than Pd/γ-alumina.
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  • 52
    ISSN: 1572-879X
    Keywords: aqueous ethanol ; multiple steady-state ; oxidation ; platinum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The selective oxidation of aqueous ethanol by dioxygen over a platinum on carbon catalyst was investigated in a three-phase continuously stirred tank reactor at a total pressure of 600 kPa, a temperature of 323 K, a pH of 8.4, and a catalyst concentration of 2.3 kg m−3. Multiple steady-states were obtained by systematic changes in the start-up procedure and variation of the feed concentration of ethanol and partial oxygen pressure in the reactor. The ethanol feed concentration was varied from 100 to 2500 mol m−3 and the partial oxygen pressure from 8 to 120 kPa. On the time scale of the experiments, i.e. 21 ks, two steady-states of the net disappearance rate of ethanol are observed in the ethanol feed concentration range from 500 to 2500 mol m−3 at a partial oxygen pressure of 58 kPa and in the range of partial pressure of oxygen from 8 to 120 kPa at an ethanol feed concentration of 500 mol m−3. Three steady-states are observed in the feed ethanol concentration range from 200 to 400 mol m−3 and a partial oxygen pressure of 58 kPa.
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  • 53
    ISSN: 1572-879X
    Keywords: TiO2 ; heterogeneous photocatalysis ; oxidation ; substituted toluenes ; zeolites
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Photocatalytic oxidation of substituted toluenes was investigated on irradiated TiO2 and TiO2 combined with HY15 and HY20 zeolites. In all cases the oxidation occurred in the first step exclusively on either one substituent or the other, but never on both simultaneously. In the presence of a zeolite, photooxidation conversion was higher than that obtained without zeolite.
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  • 54
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; cobalt catalysts ; deactivation ; oxidation ; reduction ; promoters ; rhenium
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of water on alumina-supported cobalt catalysts has been studied. The deactivation of supported Co catalysts was studied in a fixed-bed reactor using synthesis gas feeds containing different concentrations of water vapour. Supporting model studies were carried out using H2O/H2 feeds in conjunction with XPS and gravimetry. Rapid deactivation occurs on Re-promoted CO/Al2O3 catalysts when H2/CO/H2O feeds are used, whereas unpromoted CO/Al2O3 shows more stable activity. The results from the gravimetric studies suggest that only a small fraction of the bulk cobalt metal initially present reoxidizes to cobalt oxide during reaction. However, the XPS results indicate significant reoxidation of surface cobalt atoms or highly dispersed cobalt phases, which is likely to be the cause of the observed deactivation. Rhenium is shown to have a marked effect on the extent of reoxidation of alumina-supported cobalt catalysts.
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  • 55
    ISSN: 1572-879X
    Keywords: perovskite ; La1−xSrxFeO3−δ ; dehydrogenation ; oxidation ; ethane
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    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.
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  • 56
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    Catalysis letters 39 (1996), S. 205-208 
    ISSN: 1572-879X
    Keywords: oxidation ; hydroxyapatite ; carbon monoxide ; inhibition ; tetrachloromethane
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    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.
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  • 57
    ISSN: 1572-879X
    Keywords: Cl-modified Ag(111) ; oxidation ; phonons ; ethylene adsorption
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidation of Cl-modified Ag(111) under UHV conditions was investigated using AES, ISS and HREELS. The results showed that Cl-modified Ag(111) can be easily oxidized at 550 K by 1 × 10−6 mbar oxygen which was also heated to 550 K. With HREELS two fundamental vibrations at 600 and 1000 cm−1 were detected for silver oxide and the multiple losses and combination excitations as well. Ethylene adsorption on the oxide was analyzed by HREELS. Surface hydroxyl species was formed at 230 K and stable to above 300 K, which is attributed to silver oxide. Ethylidyne was suggested to form concurrently with hydroxyl species.
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  • 58
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    Catalysis letters 28 (1994), S. 53-59 
    ISSN: 1572-879X
    Keywords: coke ; zeolites ; catalyst regeneration ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The same effect of temperature on the production of CO, CO2 and H2O was found during oxidative treatment of HY zeolites either impregnated with pyrene or coked. Therefore, pyrene oxidation can be used to specify the mechanism of coke oxidation. Three types of reactions can be distinguished: (a) condensation of polyaromatic molecules, (b) oxidation of polyaromatics into aldehydes, ketones, acids and anhydrides and (c) decarbonylation or decarboxylation of oxygenated compounds, all these reactions involving protonic sites.
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  • 59
    ISSN: 1572-879X
    Keywords: platinum ; EXAFS ; catalysis ; catalyst deactivation ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract With a new set‐up for in situ EXAFS spectroscopy the state of a carbon‐supported platinum catalyst during aqueous alcohol oxidation has been observed. The catalyst deactivation during platinum‐catalysed cyclohexanol oxidation is caused by platinum surface oxide formation. The detected Pt–O co‐ordination at 2.10 Å during exposure to nitrogen‐saturated cyclohexanol solution is different from what is observed for the pure oxidised platinum surface (2.06 Å).
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  • 60
    ISSN: 1572-879X
    Keywords: catalysis ; combustion ; oxidation ; formic acid ; STM ; molecular beams ; surface diffusion ; surface reactivity ; active sites ; reconstruction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Using a combination of STM and molecular beam reactor data we summarise some important features of a model reaction (formic acid oxidation on Cu(110)) which is of general significance to surface reactivity and to catalysis. Three such features are highlighted here. The first concerns the role of weakly held species (possibly physisorbed) in surface reactions. These species, although of very short lifetime on the surface, can, nevertheless, diffuse over long distances to “find” a sparse distribution of active sites. Thus a very low coverage of oxygen on the surface of Cu(110) increases the sticking probability of all the formic acid molecules which strike the surface to high value (0.82), even though the clean surface is relatively unreactive. The important concept here is the “diffusion circle” or “collection zone” which represents the area of surface visited by the molecule in its short sojourn in the weakly held state. The second theme concerns the concept of the “flexible surface”. We show that the involvement of surface atoms in reactions directs the structure and reactivity for a particular reaction. For formic acid oxidation the liberation of Cu atoms during the removal of oxygen as water leads to gross restructuring of the surface and can lead to “compression” of one reactant (the oxygen in this case) into a lower area, higher local coverage, unreactive state (the c(6×2) oxygen structure). Thirdly, and finally, it is proposed that, for many surface reactions, the surface acts in an analogous way to a solvent, supporting a “dissolved” (highly mobile and fluxional) phase of intermediates at low coverage, which crystallise out above a critical coverage (the 2D “solubility limit”).
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  • 61
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    Catalysis letters 57 (1999), S. 109-113 
    ISSN: 1572-879X
    Keywords: superacid ; zirconia ; molybdenum oxide ; methane ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of zirconia-supported molybdenum oxide catalysts with different molybdenum loadings prepared using conditions reported to generate “superacidity” have been evaluated for their performance as catalysts for methane oxidation. A marked dependence of Mo content on activity has been observed, with the most active material being that with intermediate molybdenum content. 5 wt% MoO3/ZrO2 compares favourably with ZrxCe1-xO2 for methane combustion. The presence of MoO3 is observed to stabilise the tetragonal polymorph of ZrO2 and, as Mo content is increased, dispersed MoO3 crystallites are formed as evidenced by Raman spectroscopy. Temperature-programmed reduction studies evidence differences in the reduction behaviour of the materials as a function of loading. The results indicate that molybdenum oxide supported on monoclinic zirconia gives rise to the most active catalyst. It is tentatively suggested that the formation of a MoO3 monolayer during reaction may be of importance.
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  • 62
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    Catalysis letters 6 (1990), S. 181-186 
    ISSN: 1572-879X
    Keywords: Metals for catalysis “syngas” ; oxidation ; nickel ; platinum group metals
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Partial oxidation of methane to synthesis gas has been carried out over a number of transition metal catalysts under a range of conditions. It is found that the metals Ni, Ru, Rh, Pd, Ir and Pt, either supported on alumina or present in mixed metal oxide precursors, will bring the system to equilibrium. The yield of CO and H2 improves with increasing temperature in the range 650–1050 K, and decreases with increasing pressure between 1 and 20 atm. An excellent yield (∼92%) is obtained with a 4∶2∶1 N2∶CH4∶O2 ratio at 1050 K and atmospheric pressure, with a space velocity of 4×104 hour−1.
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  • 63
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    Catalysis letters 64 (2000), S. 113-118 
    ISSN: 1572-879X
    Keywords: X‐ray photoelectron spectroscopy (XPS) ; scanning electron microscopy (SEM) ; silver ; oxidation ; surface chemical reaction ; NO ; NO x
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The behavior of a AgNO3/Ag2O/Ag “sandwich” upon heating in vacuum was studied by in situ X‐ray photoelectron spectroscopy (XPS) and ex situ scanning electron microscopy (SEM). The AgNO3/Ag2O/Ag “sandwich” was prepared by exposure of a silver foil to a NO : O2 mixture. The upper layer of the “sandwich” consists of AgNO3 crystals of a mean size between 0.1 and 0.4 μm. Heating at 550 K in vacuum results in melting of the AgNO3 crystals. A liquid film of AgNO3, readily wetting the silver, covers the surface. Cooling below the melting point of AgNO3 leads to the agglomeration of silver nitrate to long islands with a size reaching a few tens of micrometers (μm). The possible effects of AgNO3 liquid‐phase formation on surface processes are discussed.
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  • 64
    ISSN: 1572-879X
    Keywords: chlorinated hydrocarbons ; chromia ; titania ; alumina ; CVOCs ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of perchloroethylene (PCE) was investigated over chromium oxide catalysts supported on TiO2, Al2O3, SiO2, SiO2–Al2O3 and activated carbon. The phase of chromium oxide on the catalyst surface is critical for the oxidation of PCE. The catalytic activity of PCE removal enhances as the formation of Cr(VI) species on the catalyst surface increases. The surface area and the type of the catalyst supports were also essential for high performance in the PCE oxidation. In addition, the structure of Cr(VI) on the catalyst surface also plays an important role for the decomposition of PCE. The polymerized Cr(VI) mainly formed by the interaction of metals with the support is the active reaction site for the present reaction system. CrOx/TiO2 reveals the strongest PCE removal activity among the catalysts examined in the present study.
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  • 65
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    Catalysis letters 11 (1991), S. 183-190 
    ISSN: 1572-879X
    Keywords: Three-way catalysts ; sulphur dioxide ; poisoning ; promotion ; oxidation ; steam reforming
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Over current Pt-Rh/CeO2-Al2O3 catalysts, the conversion of alkanes occurs by two principal mechanisms: direct oxidation (HC + O2) and steam reforming (HC+H2O). Sulphur dioxide can influence both these mechanisms. Direct oxidation, which predominates when the exhaust-gas is fuel-lean, ispromoted by the adsorption of SOx species by the support. Under fuel-rich atmospheres, the presence of SO2 severelyinhibits steam reforming. The poisoning is associated with the formation of S2− on the platinum and of SO 4 2− on the support, but there is no indication of S-species being retained by the rhodium. It is proposed that each of the two mechanisms is sensitive to a different type of interaction at the metal-support interface. Direct oxidation is enhanced by the transfer of electrons from the precious metal to the support; steam reforming occurs at interfacial sites, which can be blocked by adsorbed SOx species.
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  • 66
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    Catalysis letters 37 (1996), S. 79-87 
    ISSN: 1572-879X
    Keywords: methanol ; oxidation ; copper ; electron spectroscopy
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    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.
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  • 67
    ISSN: 1572-879X
    Keywords: synergistic effect ; carbon monoxide ; oxidation ; mixed oxides ; iron oxide ; tin oxide ; manganese oxide
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    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.
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  • 68
    ISSN: 1572-879X
    Keywords: non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
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    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.
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  • 69
    ISSN: 1572-879X
    Keywords: Ultraviolet heterogeneous photocatalysis ; oxidation ; trichloroethylene ; titania ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetics of the gas/solid heterogeneous photocatalytic oxidation of dilute trichloroethylene (TCE) vapors by ultraviolet-illuminated titanium dioxide have been determined using a fixed-bed dynamic photoreactor. Reaction rate dependences on inlet TCE, oxygen and water vapor concentrations were found to consist of both reactant sensitive and insensitive regions. In the reactant sensitive regions, measured limiting apparent reaction rate orders for TCE, oxygen and water vapor are 0.8, 1.7 and — 3, respectively. Water vapor in the reactant stream lowersinitial reaction rates relative to corresponding water free conditions, but is required to sustain photocatalytic activity for extended periods of time.
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  • 70
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    Catalysis letters 40 (1996), S. 47-50 
    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.
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  • 71
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    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Keywords: ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
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    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.
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  • 72
    ISSN: 1572-879X
    Keywords: oxidation ; metalloporphyrins ; hydroperoxide decomposition
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    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.
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  • 73
    ISSN: 1572-879X
    Keywords: model catalysts ; spin coating ; Pt colloid ; AFM ; XPS ; Si wafer ; particle size ; oxidation ; reduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Platinum particles of 2 nm diameter have been immobilised on oxidised silicon wafers by spin coating with colloidal solutions and characterised by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The coverage and dispersion of the Pt colloids on the Si wafer are controlled by varying the concentration and the spin speed. Under optimal conditions mono-dispersed Pt colloids on silicon wafers are prepared. For the Pt colloids immobilised on the Si wafer, the majority of the stabilising ligands are removed through a reduction (with H2 at 200°C) or an oxidation (in air at 300°C) procedure. AFM showed that particle sizes are retained after the reduction procedure, while significant sintering occurs after oxidation. The mechanism of ligand removal was studied using an in situ XPS reaction cell.
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  • 74
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    Catalysis letters 56 (1998), S. 199-202 
    ISSN: 1572-879X
    Keywords: cerium ; gas carbonic ; propane ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The interaction between CO2 and CeO2 and its role in the surface reactivity of alumina-supported cerium oxide has been studied by programmed thermodesorption (TPD) of CO2 and FTIR spectroscopy. The performance of Ce/Al2O3 systems was then analyzed for the propane oxidation in presence of CO2. The results have shown that the catalytic activity decreased when carbonate species are formed at the surface of CeO2. This behavior was attributed to the presence of CO2 from three different sources: contamination before use, during the handling of the samples, contamination proceeding from the reactants and from CO2 produced by the reaction itself.
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  • 75
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    Catalysis letters 8 (1991), S. 327-333 
    ISSN: 1572-879X
    Keywords: Platinum ; alumina ; oxichloride ; oxidation ; sintering
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Reduced Pt/Al2O3 catalysts with different chloride contents were treated at different temperatures under oxygen flow. TPR and TPD studies of oxidized species show that at low Cl/Pt atomic ratio (⩽1) PtO2 is formed at low temperature (400–500 K) and is totally decomposed (900 K) yielding reduced metallic Pt and inducing metal sintering. At high Cl/Pt atomic ratio (⩾6) formation of stable (up to 1000 K) platinum oxichloride avoids metal sintering.
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  • 76
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    Catalysis surveys from Japan 3 (1999), S. 27-35 
    ISSN: 1572-8803
    Keywords: oxidation ; oxygen ; alkane ; N‐hydroxyphthalimide ; radical catalyst
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A practical catalytic method to convert alkanes into the corresponding oxygen‐containing compounds with O2 under mild conditions using N‐hydroxyphthalimide (NHPI) in the presence or absence of a transition metal was developed. Thus, cyclohexane was successfully converted into adipic acid in good conversion and selectivity by a combined catalytic system consisting of NHPI and Mn(acac)2. Lower alkane such as isobutane was converted into t‐butyl alcohol (83%) under 10 atm of air by NHPI‐Co(OAc)2 system. Alkylbenzene such as toluene was oxidized to benzoic acid in high yield (81%) under normal temperature and pressure of dioxygen in the presence of a catalytic amount of NHPI and Co(OAc)2. ESR measurements showed that phthalimide‐N‐oxyl generated from NHPI under dioxygen atmosphere is a key species in this oxidation and functions as a radical catalyst.
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  • 77
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    Cellulose 2 (1995), S. 265-272 
    ISSN: 1572-882X
    Keywords: Hydrogen peroxide ; oxycellulose ; bleaching ; oxidation
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    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Peroxides are important bleaching agents, industrially, for cellulosic products. They are also used in detergents. Peroxides can degrade cellulose as well as decolorize it and remove stains. Both free radicals and perhydroxyl anions have been suggested as the intermediates in the reactions occurring between cellulosic products and hydrogen peroxide. The proposed mechanisms are reviewed with emphasis primarily on cotton cellulose. Further work is required to establish unequivocally the mechanism of degradation and decolorization of cellulose products.
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  • 78
    ISSN: 1432-1890
    Keywords: Key words Glomus mosseae ; Hydroponics ; Nitrate uptake ; Root respiration ; Triticum aestivum
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    Topics: Biology
    Notes: Abstract  Oxygen and CO2 fluxes were measured in hydroponically grown mycorrhizal and non-mycorrhizal Triticum aestivum L. cv. Hano roots. The NO3 – uptake of the plants was used to estimate the amount of root respiration attributable to ion uptake. Plants were grown at 4 mM N and 10 μM P, where a total and viable mycorrhizal root colonisation of 48% and 18%, respectively, by Glomus mosseae (Nicol. and Gerd.) Gerd. and Trappe (BEG 107) was observed. The O2 consumption and NO3 – uptake rates were similar and the CO2 release was higher in mycorrhizal than in non-mycorrhizal wheat. This resulted in a significantly higher respiratory quotient (RQ, mol CO2 mol–1 O2) in mycorrhizal (1.27±0.13) than in non-mycorrhizal (0.79±0.05) wheat. As the biomass and N and P concentrations in mycorrhizal and non-mycorrhizal wheat were the same, the higher RQ resulted from the mycorrhizal colonisation and not differences in nutrition per se.
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  • 79
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    Biology and fertility of soils 9 (1990), S. 281-282 
    ISSN: 1432-0789
    Keywords: Surface sterilization ; Contaminants ; Sterile plant selection ; Axenic seedlings ; Triticum aestivum ; Trifolium pratense ; Trifolium repens
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary Sterile seedlings are required for the investigation of interactions between microorganisms and plants. The present study was designed to develop a simple and reliable method for the selection of sterile seedlings by the use of liquid nutrient media, avoiding some of the disadvantages of solid media. The method of germinating surface-sterilized seedlings on solid water agar or nutrient media was compared with our method for sterility control in nutrient broth. Sterile plant selection in liquid media was the most sensitive method for detecting bacterial and fungal contaminants. Sterile plants grow with the same vigour as unsterilized plants and can be used for sterile plant experiments.
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  • 80
    ISSN: 1432-0789
    Keywords: 15N-labelled fertilizer ; Added N interaction Fertilizer N uptake ; Soil N uptake ; Wheat ; Triticum aestivum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effects of 15N-labelled ammonium nitrate, urea and ammonium sulphate on yield and uptake of labelled and unlabelled N by wheat (Triticum aestivum L. cv. Mexi-Pak-65) were studied in a field experiment. The dry matter and N yields were significantly increased with fertilizer N application compared to those from unfertilized soil. The wheat crop used 64.0–74.8%, 61.5–64.7% and 61.7–63.4% of the N from ammonium nitrate, urea and ammonium sulphate, respectively. The fertilizer N uptake showed that ammonium nitrate was a more available source of N for wheat than urea and ammonium sulphate. The effective use of fertilizer N (ratio of fertilizer N in grain to fertilizer N in whole plant) was statistically similar for the three N fertilizers. The application of fertilizer N increased the uptake of unlabelled soil N by wheat, a result attributed to a positive added N interaction, which varied with the method of application of fertilizer N. Ammonium nitrate, urea and ammonium sulphate gave 59.3%, 42.8% and 26.3% more added N interaction, respectively, when applied by the broadcast/worked-in method than with band placement. A highly significant correlation between soil N and grain yield, dry matter and added N interaction showed that soil N was more important than fertilizer N in wheat production. A values were not significantly correlated with added N interaction (r=0.719). The observed added N interaction may have been the result of pool substitution, whereby added labelled fertilizer N stood proxy for unlabelled soil N.
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  • 81
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    Biology and fertility of soils 23 (1996), S. 327-331 
    ISSN: 1432-0789
    Keywords: CO2 emission ; Field method ; Soil respiration ; Triticum aestivum ; Soil moisture ; Carbon reservoirs ; Greenhouse effect ; Grey forest soil ; Mineralization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The dynamics of the rate of CO2 evolution from soil in fallow and croplant under spring wheat (Triticum aestivum L.) was studied in a crop rotation in grey forest soil of the Baikal forest-steppe during the growing season and in different years. It was shown that the regional characteristics of soils and hydrothermal conditions in different years affect the rate of CO2 evolution in agroecosystems. The seasonal dynamics of CO2 is characterized by insignificant changes in the autumn to spring period and enhanced emission in hot and dry summers. CO2 evolution is assumed to increase due to enhanced mineralization and partial diffusion from the carbonate horizon at the depth of the seasonal frost. During the growing season the dynamics of CO2 evolution depends on the soil moisture regime. There was a strong correlation between the rate of CO2 emission and soil moisture in the particularly dry year of 1993 (η=0.86) and a moderate correlation in the other years (η=0.38–0.54). The effect of the previous crop and fertilizer application on the rate of CO2 emission was insignificant. In a continuous fallow the total carbon release into the atmosphere varied throughout the years studied from 558 to 1880 kg ha-1. Humus losses varied from 0.9% to 3.1%.
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  • 82
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    Biology and fertility of soils 23 (1996), S. 327-331 
    ISSN: 1432-0789
    Keywords: Key words CO2 emission ; Field method ; Soil respiration ; Triticum aestivum ; Soil moisture ; Carbon reservoirs ; Greenhouse effect ; Grey forest soil ; Mineralization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The dynamics of the rate of CO2 evolution from soil in fallow and cropland under spring wheat (Triticum aestivum L.) was studied in a crop rotation in grey forest soil of the Baikal forest-steppe during the growing season and in different years. It was shown that the regional characteristics of soils and hydrothermal conditions in different years affect the rate of CO2 evolution in agroecosystems. The seasonal dynamics of CO2 is characterized by insignificant changes in the autumn to spring period and enhanced emission in hot and dry summers. CO2 evolution is assumed to increase due to enhanced mineralization and partial diffusion from the carbonate horizon at the depth of the seasonal frost. During the growing season the dynamics of CO2 evolution depends on the soil moisture regime. There was a strong correlation between the rate of CO2 emission and soil moisture in the particularly dry year of 1993 (η=0.86) and a moderate correlation in the other years (η=0.38–0.54). The effect of the previous crop and fertilizer application on the rate of CO2 emission was insignificant. In a continuous fallow the total carbon release into the atmosphere varied throughout the years studied from 558 to 1880 kg ha–1. Humus losses varied from 0.9% to 3.1%.
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  • 83
    ISSN: 1432-0789
    Keywords: Key words Phosphate-solubilizing microorganisms ; Mussoorie rock phosphate ; Vesicular-arbuscular mycorrhizae ; Triticum aestivum ; Nutrient-deficient soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  The effect of inoculating wheat (Triticum aestivum L.) with the PO4 3–-solubilizing microorganisms (PSM) Bacillus circulans and Cladosporium herbarum and the vesicular-arbuscular mycorrhizal (VAM) fungus Glomus sp. 88 with or without Mussoorie rock phosphate (MRP) amendment in a nutrient-deficient natural sandy soil was studied. In the sandy soil of low fertility root colonization by VAM fungi was low. Inoculation with Glomus sp. 88 improved root colonization. At maturity, grain and straw yields as well as N and P uptake improved significantly following inoculation with PSM or the VAM fungus. These increases were higher on combined inoculation of PSM and the VAM fungus with MRP amendment. In general, a larger population of PSM was maintained in the rhizosphere of wheat in treatments with VAM fungal inoculation and MRP amendment. The results suggest that combined inoculation with PSM and a VAM fungus along with MRP amendment can improve crop yields in nutrient-deficient soils.
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  • 84
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    Biology and fertility of soils 23 (1996), S. 273-281 
    ISSN: 1432-0789
    Keywords: Wheat ; Triticum aestivum ; Rhizosphere ; Soil microflora ; Gram-negative bacteria ; API 20 NE ; Flavobacterium spp ; Cytophaga
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract We identified 161 Gram-negative bacterial strains isolated from the root surface of wheat grown under different soil conditions. The strains were divided into seven groups based on major morphological and physiological properties. Taxonomic allocation of the groups was verified by guanine+cytosine contents of DNA. Except for one group, which may be assumed to include bacteria belonging to the genera Flavobacterium and Cytophaga, the various groups were taxonomically united. The distribution of the groups changed with soil improvement. Pseudomonads predominated in unimproved soil, but Flavobacterium and Cytophaga spp. were predominant in the most improved soil. As all the strains were non-fermentative by Hugh and Leifson's test, API 20NE identification was applied. However, many strains were misidentified by this system, especially in the Flavobacterium and Cytophaga spp. group. For ecological studies, the strains were classified to species level by the API 20 NE system and by the results of a combination of guanine+cytosine (mol%) and isoprenoid quinone data. The pattern of distribution of the bacteria on the root surface of wheat varied at species level within one genus depending on soil conditions.
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  • 85
    ISSN: 1432-0983
    Keywords: Secale cereale ; Triticum aestivum ; Ribosomal RNA genes ; Mitochondrial DNA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The mitochondrial 18S and 5S ribosomal RNA (rRNA) genes of rye, plus a total of about 90 kilobase pairs of flanking DNA, have been cloned and maps of restriction enzyme cleavage sites have been constructed. Like their homologs from hexaploid wheat, the rye genes are closely linked and are part of a three-copy family of recombining repeats (the “18S/5S repeat”). The rye repeat probably also contains a mitochondrial tRNAfMet gene, which the wheat repeat is known to carry. However, despite the overall organizational similarity between the wheat and rye 18S/5S repeats in the immediate vicinity of their coding regions, extensive rearrangement of flanking sequences has taken place during evolutionary divergence of the two species. Our data provide additional support for an emerging picture of plant mitochondrial genomes as evolving much more rapidly in structure than in sequence.
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  • 86
    ISSN: 1432-0983
    Keywords: Light regulation ; psbN ; Triticum aestivum ; Etioplast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The nucleotide sequence of a region of wheat chloroplast DNA containing the psbB gene for the 47 kDa chlorophyll a-binding protein of photosystem II has been determined. The gene encodes a polypeptide of 508 amino acid residues which is predicted to contain six hydrophobic membrane-spanning regions. The psbB gene is located 562 bp upstream of the psbH gene for the 10 kDa phosphoprotein of photosystem II. A small open reading frame of 38 codons is located between psbB and psbH, and on the opposite strand the psbN gene, encoding a photosystem II polypeptide of 43 amino acid residues, is located between orf38 and psbH. S1 nuclease mapping indicated that the 5′ ends of transcripts were located 371 and 183 bp upstream of the psbB translation initiation codon. Predominant transcripts of 2.1 kb and 1.8 kb for psbB and 0.4 kb for psbH were present in RNA isolated from etiolated and greening wheat seedlings. Immunodecoration of Western blots indicated that the 47 kDa polypeptide was absent, or present in very low amounts, in dark-grown tissue and accumulated on greening, whereas the 10 kDa polypeptide was present in similar amounts in both dark-grown and greening seedlings. The 10 kDa polypeptide was phosphorylated in vitro by incubating wheat etioplast membranes with [γ3 2P] ATP.
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  • 87
    ISSN: 1432-0983
    Keywords: Triticum aestivum ; Mitochondrial DNA ; Chloroplast DNA ; ATPase alpha subunit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary An internal part of the chloroplast atpA gene has been identified in the mitochondrial DNA of Triticum aestivum. It is located near the 18S-5S ribosomal genes and partially contained within a repeated sequence. Comparison of the transferred sequence with the original ct sequence reveals several nucleotide changes and shows that neither 5′ nor 3′ ends are present in the mt genome. No transcript of this region could be detected by Northern analysis. This sequence is present in mitochondrial genomes of other tetraploid and diploid species of Triticum, also in the vicinity of the 18S-5S ribosomal genes, suggesting a unique transfer event. The date of this event is discussed.
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  • 88
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    Journal of solid state electrochemistry 3 (1999), S. 179-186 
    ISSN: 1433-0768
    Keywords: Key words Cathodic protection system ; Carbon ; oxidation ; Composite carbon/polymer anode ; Lifetime
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The suitability of a polymeric composite material for use as part of an anode structure in a cathodic protection system has been examined. The composite material was a conductive blend (volume resistivity typically 1.5 Ω cm) of carbon black in a polyethylene binder. A long operational lifetime for the material demands that the rate of carbon loss must be low. In the work reported here, electrochemical and in situ analytical techniques were employed to characterise the performance of the material over a wide range of anodic current densities in a variety of aqueous electrolytes. The predominant anodic electrochemical reaction on the polymeric material is CO2 formation in acid and neutral solutions, which causes loss of carbon from the surface and the development of a non-conducting layer of polyethylene. The characteristics of the reaction suggest that it occurs via the discharge of H2O. In alkaline pH, however, the anodic reactions are more complex. A high OH− concentration (pH 12 or higher) favours the formation of oxygen rather than CO2, particularly at low anodic potentials. The presence of CO3 2− in the electrolyte catalyses the evolution of oxygen at pH values as low as 9. The electrochemical formation of oxygen always occurs in parallel with the generation of some humic acid in the solution.
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  • 89
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    European journal of nutrition 36 (1997), S. 336-339 
    ISSN: 1436-6215
    Keywords: Amino acids ; protein ; metabolism ; meal feeding ; oxidation ; breath test ; Aminosäuren ; Protein ; Stoffwechsel ; Fütterung ; Oxidation ; Atemtest
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Medicine
    Description / Table of Contents: Zusammenfassung Die aktuellen Mengen an freien Aminosäuren im Blut reichen nur aus, um die Ganzkörper-Proteinsynthese für einige Minuten aufrecht zu erhalten. Das zeigt, daß die freien Aminosäurenkonzentrationen in der Zirkulation klein und konstant gehalten werden im Vergleich zu den Mengen der Aminosäuren, die täglich aufgenommen und über die Körperproteine umgesetzt werden. Das Verschwinden der Aminosäuren exogenen oder endogenen Ursprungs aus dem freien Aminosäuren-Pool, findet hauptsächlich durch die Proteinsynthese und den Aminosäurenabbau statt. Die Partitionierung der Nahrungs-Aminosäuren zwischen diesen beiden Prozessen im Kurzzeitbereich werden als bedeutsam für die Ökonomie der Ganzkörper-Aminosäuren angesehen. Eine Verbesserung der Aminosäurenökonomie könnte durch solche nutritiven Maßnahmen erreicht werden, welche die Clearance der Nahrungsaminosäuren durch die Proteinsynthese anstelle des Aminosäurenabbaus begünstigen. Diese nutritiven Maßnahmen sollten sich an den „Schwellenwerten“ des Abbaus der individuellen Aminosäuren orientieren.
    Notes: Summary Actual amounts of free amino acids in the blood are sufficient to support whole body protein synthesis for some minutes only. This indicates that the levels of free amino acids in the circulation are kept small and constant relative to the amounts of amino acids supplied by daily intake and turnover of body proteins. The clearance of the amino acids originating from either endogenous or exogenous sources is mainly due to protein synthesis and metabolic degradation. The partitioning of dietary amino acids between these processes, on the short term, is supposed to play an important role in whole body amino acid economy. Therefore whole body amino acid economy could be improved by nutritional measures that favour the clearance of dietary amino acids by protein synthesis instead of by metabolic degradation. These nutritional measures should to be focused on threshold values for metabolic degradation of individual amino acids.
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  • 90
    ISSN: 1436-5073
    Keywords: manganese(III) ; pyrophosphate ; oxidation ; hydrazines ; hydrazides ; carbazides ; potentiometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Manganese(III) ion was stabilised in weakly acidic solution by means of pyrophosphate. Conditions for the quantitative oxidation of hydrazine, benzoylhydrazines, aroxyacetylhydrazines, semicarbazide, semicarbazones, thiosemicarbazide and thiosemicarbazones were investigated by titrimetric and potentiometric methods. The stoichiometries of these oxidations were pH-dependent. At pH 5 benzoyl hydrazines were oxidised by donating two electron each, the nitro derivative being the sole exception to show a three-electron change. Aroxyacetylhydrazines, semicarbazide and semicarbazones underwent three-electron oxidations. The free radical nature of these reactions was illustrated. Thiosemicarbazides reacted faster than semicarbazides. Metal complexes of thiosemicarbazide also yielded stoichiometric results, indicative of the number of TSC ligands in the complex. The oxidation products have been identified. At pH ⩽ 1 these reactions conformed to different stoichiometries.
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  • 91
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    Microchimica acta 102 (1990), S. 271-276 
    ISSN: 1436-5073
    Keywords: mercaptans ; oxidation ; disulphide ; Chlorobenzotriazole ; potentiometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A simple but accurate potentiometric method for the estimations of mercaptans in 0.01M perchloric acid has been developed, based on their oxidation with 1-Chlorobenzotriazole. Quantitative oxidation solely to the disulphide stage is ensured by using critical amounts of methanol, acetonitrile and potassium iodide. Chloride, mercury(II) and copper(II) interfere. A back-titration procedure can also be used. The oxidation products have been identified.
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  • 92
    ISSN: 1436-5073
    Keywords: oxidation ; titanium aluminide ; SNMS ; niobium effect ; oxygen tracer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation behaviour of γ-TiAl based alloys with different Nb contents (2–10 At.%) was investigated in air and in argon-20% oxygen at 900 °C using thermogravimetric analysis. The oxide scales were characterized by a combination of optical microscopy, SEM/EDX and X-ray diffraction analyses. Although in all studied cases the presence of niobium improves the oxidation resistance of γ-TiAl, the oxidation kinetics, scale morphology and composition in air differed strongly from that in argon-oxygen. In air the oxidation resistance increases with increasing niobium-content. In Ar/O2 the niobium dependence is far more complex because internal oxidation occurs which is favoured by the presence of niobium. SNMS analysis revealed that the differences in behaviour in the two atmospheres are related to the formation of Ti-rich nitride at the scale/alloy interface during air oxidation. The positive effect of niobium on the oxidation resistance of γ-TiAl is mainly caused by a decrease of the transport processes in the heterogeneous TiO2/Al2O3-surface scale. Nitride formation and/or niobium enrichment at the scale/alloy interface also affect the oxidation behaviour, however these factors are believed to be the result of the decreased transport processes rather than the main reason for the niobium effect.
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  • 93
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    Microchimica acta 125 (1997), S. 401-406 
    ISSN: 1436-5073
    Keywords: fullerenes ; intercalation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The investigation of structural and electronic properties of the novel family of fullerenes depends on the existence of pure reference materials. Sublimation of the van-der Waals solids is a suitable purification method. Little attention has been paid to the question about the air stability of such sublimed samples in form of crystals or thin films. A combination of thermal desorption spectroscopy, thermal analysis and diffuse reflectance FT-IR spectroscopy is used to show the extent to which oxygen from dry air is intercalated into fullerenes and which detrimental reactivity occurs from attempts to thermally remove („nneal”) air-exposed samples. The conclusion is that any fullerene sample exposed to air will be transformed in part into a polymeric non-fullerene carbon upon thermal treatment to above 400 K irrespective of its initial purity.
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  • 94
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    Nutrient cycling in agroecosystems 35 (1993), S. 101-114 
    ISSN: 1573-0867
    Keywords: Elemental sulfur ; oxidation ; S fertilizers ; thiobacilli ; heterotrophic S-oxidizers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The use of elemental sulfur (S0) to alleviate widespread S deficiencies in agricultural soils is limited by the unpredictability of its oxidation to plant available sulfate. Here we review the biological, fertilizer and soil-related factors that control S0 oxidation. Sulfur oxidation in soil is mediated primarily by microorganisms, and thus it is the size, composition and activity of the microbial community which dictate oxidation rates. Because S0 oxidation is a biological process, it is strongly influenced by factors directly affecting microbial activity including soil temperature, water potential, and aeration. In many soils these factors represent the primary constraints to S0 oxidation. Oxidation is also influenced by the effective surface area of the S exposed to microbial activity. Thus oxidation is favored by reducing the particle size and abundant populations of heterotrophic bacteria and fungi capable of oxidizing S0, thus the availability of organic substrates from residue additions or root exudates may also affect S oxidation. Previous application of S0 may increase oxidation rates in many soils, presumably by stimulating S0 oxidizing populations. The large number of factors that govern S0 oxidation account for the variability in oxidation rates among soils, climatic regions, and agronomic practices. Many of these factors are subject to agronomic control, however, and it should be possible to devise S fertilizer strategies that exploit the slow release characteristics of S0 to meet crop demands efficiently in a variety of conditions.
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  • 95
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    Nutrient cycling in agroecosystems 40 (1994), S. 207-214 
    ISSN: 1573-0867
    Keywords: available P ; citrate insoluble P ; phosphorus sources ; triple superphosphate ; Triticum aestivum ; water soluble P ; wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A greenhouse study was conducted to determine if soil pH affects the requirement for water-soluble P and the tolerance of water-insoluble impurities in TSP fertilizers. Two commercial TSP fertilizers were selected to represent a range in phosphate rock sources and impurities. Phosphate fertilizer impurities were isolated as the water-washed fraction by washing whole fertilizers with deionized water. TSP fertilizers with various quantities of water-soluble P (1.2 to 99% water-soluble P) were simulated by mixing the water-washed fertilizer fractions or dicalcium phosphate (DCP) with reagent-grade monocalcium phosphate (MCP). The fertilizers were applied to supply 40 mg AOAC available P kg−1 to a Mountview silt loam (fine-silty, siliceous, thermic Typic Paleudults). Wheat (Triticum aestivum (L.)) was harvested at 49 and 84 days after planting. Soil pH values at the final forage harvest were 5.4±0.16 and 6.4±0.15. At a soil pH of 5.4, the TSP fertilizers required only 37% water-soluble P to reach maximum yields while at pH 6.4 the fertilizers required 63% water-soluble P. Results of this study show that higher levels of water -insoluble P can be tolerated in TSP fertilizers when applied to acid soils. Phosphorus uptake was not affected by soil pH, but for the mixtures containing the fertilizer residues the source having the lowest level of Fe and Al had a higher relative agronomic effectiveness.
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    Nutrient cycling in agroecosystems 53 (1999), S. 157-175 
    ISSN: 1573-0867
    Keywords: Brassica napus ; Cicer arietinum ; current P ; Lens culinaris ; Lupinus albus ; Lupinus angustifolius ; P concentration response ; P content response ; Pisum sativum ; previous P ; sigmoid response ; single superphosphate ; Triticum aestivum ; Vicia faba ; yield response
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Phosphorus (P) is a major deficiency of soils of south-western Australia (WA). The fertilizer P requirements are not known for grain legumes being evaluated for neutral to alkaline, fine textured soils in WA. To rectify this, glasshouse and field experiments were undertaken to compare the responses of several grain legume species, wheat and canola to applications of single superphosphate and the results are reported in this paper. The glasshouse experiments measured responses of dried tops, harvested at 26 to 42 days after sowing, to P that was freshly-applied (current P) and previously-applied (previous P). Responses in the glasshouse were measured using yield, P concentration and P content (P concentration multiplied by yield) of oven dried tops of the following: wheat (Triticum aestivum), canola (Brassica napus), faba bean (Vicia faba), chickpea (Cicer arietinum), lentil (Lens culinaris), field pea (Pisum sativum), albus lupin (Lupinus albus) and narrow leaf lupin (Lupinus angustifolius). Field experiments in 1994 and 1995 compared seed (grain) yield responses of faba bean, chickpea, lentil, albus lupin and wheat to applications of current P. The P was banded (drilled) with the seed while sowing at 5 cm depth. Canola and wheat produced very large yield responses to increasing applications of current P. Responses were much smaller for albus lupin, faba bean and chickpea. Responses for lentil, narrow leaf lupin and field pea, fell in between responses of the small and large seeded species. Similar trends for responses were obtained as measured using yield, P concentration, or P content. For soils treated with previous P, similar trends were observed as for current P, but differences in yield responses between species were much less marked and the response curves tended to become more sigmoid. In the field experiments, grain yield responses to current P of albus lupin and chickpea were less than that for wheat. Relative to wheat, faba bean was the most responsive grain legume to applications of current P, with lentil producing similar responses to wheat in one experiment at a newly cleared, P deficient site.
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    Nutrient cycling in agroecosystems 56 (2000), S. 59-68 
    ISSN: 1573-0867
    Keywords: bicarbonate-extractable potassium ; muriate of potash ; potassium ; potassium chloride ; relative effectiveness ; silicate rock powder ; Triticum aestivum ; Trifolium subterraneum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Granite (silicate) rock dust, a by-product of quarry operations, is being advocated and used as a fertilizer in the wheatbelt of south-western Australia (WA). The dust is insoluble and based on its nutrient element content (1.9% K and 0.3%P and negligible N) it is not expected to be a useful fertilizer. Previous laboratory studies and glasshouse experiments in WA suggest the dust is a slow release K fertilizer. This paper extends the previous studies to consider the dust as an NP or K fertilizer in the year of application in a field experiment on a soil deficient in N, P and K. In addition, the effectiveness of the dust as a K fertilizer was compared with the effectiveness of KCl (muriate of potash), the K fertilizer used in WA at present, in glasshouse experiments using K deficient soils. In the field experiment, compared with NP fertilizer or NPK fertilizer (urea, supplying N; superphosphate, providing P, S, Ca, Cu, Zn and Mo; KCl providing K), the dust had no effect on grain yield of wheat (Triticum aestivum); in fact dust applied at 20 t ha-1, for unknown reasons, reduced yields by about 65% compared to the nil (no fertilizer, no dust) treatment. Relative to the nil treatment, applying NPK fertilizer increased yields about threefold, from 0.54 to 1.79 t ha. The glasshouse experiments showed that, relative to KCl, the dust was from about 0.02 to 14% as effective in K deficient grey sandy soils for producing dried tops of 30-day old wheat plants or 42-day old clover (Trifolium subterraneum) plants. In soils with adequate K (yellow sands, sandy loams or clays, loamy clays, clay loams and clays), neither KCl nor the dust affected yields of 30 to 42-day old wheat or clover plants grown in the glasshouse. In the glasshouse experiments, no yield depressions were measured for the dust applied up to 17 g dust per kg soil (equivalent to 17 t dust ha-1 mixed into the top 10 cm of soil in the field). It is concluded that the dust has no value as a fertilizer.
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    Nutrient cycling in agroecosystems 56 (2000), S. 117-123 
    ISSN: 1573-0867
    Keywords: labelled nitrogen ; Lolium perenne ; nitrogen cycling ; root biomass ; straw ; Triticum aestivum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Large amounts of nitrogen (N) fertiliser (150–200 kg N/ha) are currently being applied to perennial ryegrass (Lolium perenneL.) seed crops in New Zealand. Due to increasing requirements for efficient use of N fertilisers and minimising nitrate contamination of the environment, a field experiment was established using 15N-labelled fertiliser to follow the fate of applied N. Urea-15N was applied to a perennial ryegrass seed crop in April (30 kg N/ha), August (30 kg N/ha), September (60 kg N/ha) and October (60 kg N/ha). The urea-15N was applied in solution and watered in to minimise volatilisation loss. At the time of harvest (December), 9% of the applied 15N was in the seed, 29% in the straw, 19% in the roots and 39% in the soil organic matter. Losses of 15N were minimal as the N was applied in several applications, each one at a relatively low rate, and at times when leaching was unlikely to occur. Ryegrass plants used a greater proportion of the N applied in September and October (61–65%) compared with that applied in April (44%). Consequently more N was recovered from the soil in the autumn application (57%) than from the September and October applications (28–44%). The availability of the residual fertiliser N to a subsequent wheat (Triticum aestivum L.) crop was studied in a glasshouse experiment. The residual fertiliser N was present in the soil and ryegrass roots and stubble. The wheat plants only recovered 7–9% of this residual N. Most of the N taken up by the wheat came from the soil organic N pool. Overall, applying a total of 180 kg N/ha to the ryegrass appeared to have minimal direct impact on the environment. In the short term N not used by the ryegrass plants contributed to the soil organic N pool.
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    Nutrient cycling in agroecosystems 35 (1993), S. 115-126 
    ISSN: 1573-0867
    Keywords: Elemental sulfur ; shape ; size ; size distribution ; model ; oxidation ; rate ; soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Direct and recursive estimation models for the oxidation rate of elemental sulfur (S°) in soil have been proposed, both essentially based on a constant oxidation rate per unit area of exposed surface. Fertilizer S° is taken to consist largely of blocky shaped particles, i.e. having similar dimensions along three axes, which can be treated as equivalent spheres. The most important implication in applying the rate assumption to these shaped particles is that the mass at any time is related to the cube of the time. This has been verified experimentally for oxidation by thiobacilli. Although the assumption is less likely for heterotrophs, experiments involving four soils conformed to the cubic relation. Implications for the particle variables of size and size distribution have been given more limited testing. The data are generally consistent with theory, such as independence of the rate constant with particle size. Assuming an activation energy for the oxidation process implies, in addition to the above, an exponential relation of rate constant with temperature. This is supported by experiment. Values for the activation energy are approximately 85 kJ mol−1, and therefore consistent with the rate limiting step for the oxidation being a chemical or biochemical reaction, rather than a diffusion process. Because absolute rate constants are generated by the models, they are useful for examining the effects of environmental variables not hitherto included. Empirical relationships, once established, can then be included in the model, such as the quadratic relation between rate constant and soil moisture, with the maximum at approximately field capacity. The delay time (the time to reach maximum oxidation rate) was useful, together with the rate constant, for distinguishing species of oxidizing microorganisms. Typically, under optimum conditions at 25°C, thiobacilli have a delay time of several days and a rate constant of 50µg cm−2 day−1 S, while heterotrophs have a negligible delay time but a rate constant of only 5µg cm−2 day−1 S. The cubic model with a single rate constant gave a surprisingly good fit to the oxidation rate over 12 months in New Zealand pastoral soils under field conditions of varying temperature and moisture. This was attributed to the balancing effect of moisture and temperature on the rate constant under the cool temperate climate. A knowledge of the annual average soil temperature is sufficient to provide advice on the optimum particle size for S° fertilizer.
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  • 100
    Electronic Resource
    Electronic Resource
    Springer
    Nutrient cycling in agroecosystems 39 (1994), S. 43-57 
    ISSN: 1573-0867
    Keywords: Bicarbonate soil test phosphorus ; relative effectiveness ; rock phosphate ; superphosphate ; Triticum aestivum ; ×Triticosecale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effect of water supply on the response of wheat (Triticum aestivum) and triticale (×Triticosecale) to levels of freshly-applied rock phosphate and superphosphate, and the residues of these fertilizers applied 9 years previously in the field, was studied in three glasshouse experiments. The 〈 2 mm fraction of the top 10 cm of soil was used (1.8 kg soil per pot), and in one experiment, freshly-applied fertilizer was also added to the more acidic subsoil (10 to 20 cm). There were two water treatments: the soil was returned to field capacity by watering to weight, either daily (W1, adequate water) or weekly (W2, water stress). Yield of dried tops was used to calculate fertilizer effectiveness. The phosphorus (P) concentration in dried tops was used to determine critical P, which is the P concentration related to 90% of the maximum yield. Just before sowing, soil samples were collected to measure bicarbonate-extractable (soil test) P which was related to plant yield. Water stress reduced yields and maximum yield plateaus by 20 to 40%. Water stress reduced the effectiveness of all P fertilizers by between 20 to 60%, largely because of a reduction in the maximum yield potentials. In the field, water supply is seasonally dependent and it can affect the yield response of plants to freshly-applied rock phosphate and superphosphate and the residues of these fertilizers applied to the field in previous years. Relative to placing fertilizer in the topsoil, placing fertilizer in the subsoil improved effectiveness by about 26% for rock phosphate and 12% for superphosphate. The relationship between yield and P concentration in dried tops, and critical P, differed for W1 and W2. The soil test P calibration, which relates yield to soil test P, and the soil test P required to produce the same yield also differed for W1 and W2. Consequently critical P and soil test P calibrations depend on water supply, which in the field varies within and between growing seasons. This is so for freshly- and previously-applied rock phosphate and superphosphate.
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