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  • 1
    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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  • 2
    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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  • 3
    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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  • 4
    ISSN: 1572-879X
    Keywords: Fe/HZSM-5 zeolite catalysts ; carbon monoxide hydrogenation ; infrared spectra of chemisorbed pyridine ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Iron catalysts supported on ZSM-5 zeolites of a wide range of silica-to-alumina ratios (29-∞) have been prepared and tested in carbon monoxide hydrogenation. The crystalline phases of the catalysts were characterized by X-ray diffraction and their acidity by infrared spectroscopy of adsorbed pyridine. The catalytic tests were conducted at 533 K, an overall pressure of 21 bar and a feed ratio CO/H2 close to 1. It was found that the selectivity to light olefins (C2–C4) increases in parallel with the increase of the Si/Al ratio of the zeolite. This was explained in terms of the decrease in Brønsted acidity of the catalysts. As a consequence, very high olefin selectivities can be achieved by decreasing the number of strong acid sites in the zeolite structure, but at the expense of high oxygenate formation.
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  • 5
    ISSN: 1572-879X
    Keywords: Methane ; formaldehyde ; oxidation ; vanadium oxide ; silica
    Source: Springer Online Journal Archives 1860-2000
    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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  • 6
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    Catalysis letters 21 (1993), S. 309-320 
    ISSN: 1572-879X
    Keywords: Sol-gel catalysts ; platinum-tin catalysts ; platinum dispersion ; X-ray diffraction ; energy dispersive X-ray analysis ; EDX analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Highly dispersed platinum was found in Pt-Sn/Al2O3 catalysts prepared by the sol-gel method, i.e., cogelation of aluminum tri-sec-butoxide and tetrabutyltin and subsequent impregnation with hexachloroplatinic acid. X-ray diffraction studies showed that the cell parameter of pure platinum is not modified in bimetallic Pt-Sn samples. Moreover, energy dispersive X-ray analysis studies (EDX) showed that platinum, but not tin, was detected in the catalysts where tin was incorporated by the sol-gel coprecipitation of tin and aluminum. Incorporation of tin into the alumina network is suggested.
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  • 7
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; calcium-based catalysts ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    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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  • 8
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; strontium hydroxyapatite ; lead hydroxyapatite ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    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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  • 9
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    Catalysis surveys from Japan 3 (1999), S. 55-60 
    ISSN: 1572-8803
    Keywords: acetic acid ; oxidation ; Pd ; heteropoly acid ; ethylene
    Source: Springer Online Journal Archives 1860-2000
    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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  • 10
    ISSN: 1572-8927
    Keywords: Manganese chloride ; cobalt chloride ; nickel chloride ; X-ray diffraction ; saturated solution ; structure of complex ; growth unit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract As a part of our studies on crystallization processes of electrolytes, the structure of aqueous solutions of MCl2 (M = Mn, Co, Ni) equilibrated with hydrate crystals, MCl2 · mH2O (m = 6, 4, 2), was investigated by means of X-ray diffraction at 25, 40, 55, and 70°C. The complexes formed in MnCl2 solutions, were found to be mixed–ligand chloroaqua octahedral complexes of M2+ ions with the Mn—O and Mn—Cl distances of about 220 and 251 pm, respectively. The average number of Mn—Cl and Mn—O interactions increased from 1.2 to 1.9 and decreased from 4.8 to 4.1, respectively, with changing MnCl2 solutions from Mn25 (MnCl2 solution at 25°C) to Mn70 (MnCl2 solution at 70°C). In the octahedral species of Co2+, the Co—O and Co—Cl distances were found to be about 211 and 240 pm, respectively. With an increase in the saturated concentration by changing temperature from 25 to 70°C, the average coordination number of the Co—Cl contact per Co2+ increased from 0.5 to 1.2, and the average number of Co—O interactions decreased from 5.5 to 4.8. The structural analysis was carried out by taking into consideration the existence of the tetrahedral species in the solutions saturated at 40, 55, and 70°C, on the assumption of the existence of [CoCl4]2−. The Co—Cl distance was found to be 228 pm, while the number of Co—Cl interactions in the [CoCl4] complex was calculated to be 3.7 by the least-squares calculations. The Ni—O and Ni—Cl distances were estimated to be about 206 and 237 pm, respectively. The frequency factor n of the Ni—O and Ni—Cl interactions decreased monotonously from 5.6 to 5.0 and increased from 0.4 to 1.0, respectively, with increasing NiCl2 concentration. The n values of the Co—Cl and Ni—Cl interactions of the octahedral complexes increased sharply with concentration at higher concentrations. Comparing structures of the complexes in the saturated solutions and the hydrate crystals of these metal ions, we discussed a role of the complexing species on crystallization of the hydrates.
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  • 11
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    Journal of polymer research 6 (1999), S. 51-58 
    ISSN: 1572-8935
    Keywords: Aromatic polyimides ; X-ray diffraction ; Molecular mechanics modeling ; Crystal unit cell ; Correlation length ; Paracrystalline distortion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract X-ray diffraction and molecular mechanics modeling have been used to investigate the structures of aromatic polyimides. The polyimides are synthesized by the reaction of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB), 3,3′-dimethyl-4,4′-diaminobiphenyl or o-tolidine (OTOL) and 2,2′-dimethyl-4,4′-diaminobiphenyl (DMB). PFMB, OTOL and DMB contain the same biphenyl structure, but the pendent groups are different or are at different positions. In the present paper, we describe the effect of pendent groups on the crystal structure and the drawability for these polymers. The crystal structures are triclinic unit cell with a=17.49 Å, b=19.94 Å, c=20.43 Å, α=40.7°, β=74.5° and γ=79.4° for homopoly(BPDA-OTOL) and triclinic unit cell with a=16.46 Å, b=9.60 Å, c=40.6 Å, α=90°, β=46°, and γ=79.4° for homopoly(BPDA-DMB). The homopoly(BPDA-OTOL) fibers can be drawn into ×2. Higher draw ratio of homopoly(BPDA-OTOL) fibers were not obtained because of thermal degradation. The other two homopolymers can be drawn from ×2 upto ×10. The increasing draw ratios are accompanied with a decrease of paracrystalline distortion and an increase of correlation length as well as degree of orientation. These are probably due to the presence of more flexible polymer chains of homopoly(BPDA-PFMB) and homopoly(BPDA-DMB), which increase the perfection of polymer chain arrangements during drawing.
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  • 12
    ISSN: 1572-8935
    Keywords: Liquid side chain crystalline copolysiloxane polymers ; Microstructure ; X-ray diffraction ; Differential scanning calorimetry ; Solid state NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract This manuscript proposes a packing arrangement model for a co-mesogenic sidechain liquid crystalline copolysiloxane polymer copoly[4-allyloxy-benzoic acid [4′-2-(2-methoxyethoxy) ethoxy] biphenyl]-4-y1 ester-co-4-allyloxy-[(4-cyano)-4′-phenyl] carboxyl benzoate ester (copoly [(MS3BDBE2)-co-(MCN)]x/y depending on the relative molar composition of each mesogen. From the analysis of the thermal data, X-ray diffraction data, and solid state NMR spin-lattice relaxation (T1ρ H) data, we have found two side chain molecules in the mesophase layer coming from the same or a different polymer backbone. They are presumed to be mixed and form a bilayer smectic C mesophase at lower MCN concentrations as well as at higher MCN concentrations.
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  • 13
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    Catalysis letters 57 (1999), S. 109-113 
    ISSN: 1572-879X
    Keywords: superacid ; zirconia ; molybdenum oxide ; methane ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    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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  • 14
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    Catalysis surveys from Japan 3 (1999), S. 27-35 
    ISSN: 1572-8803
    Keywords: oxidation ; oxygen ; alkane ; N‐hydroxyphthalimide ; radical catalyst
    Source: Springer Online Journal Archives 1860-2000
    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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  • 15
    ISSN: 1433-0768
    Keywords: Key words Lithium battery ; Anode ; Amorphous tin composite oxides ; X-ray diffraction ; Infrared spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Tin-based composite oxide materials have received considerable attention as potential anode materials for rechargeable lithium batteries. In this contribution we present the results of our investigations of the SnOB2O3P2O5 system. We have investigated its electrochemical properties and especially its cycling performance. A focus of our interest was to explain the structural changes which occur during lithium cycling and their strong dependence on the preparation method. A part of the SnO component was converted into a very stable metallic phase. In addition, a decrease was observed in capacity owing to the formation of isolated and inactive tin grains. We also report on structural changes in the B2O3P2O5 matrix.
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  • 16
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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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  • 17
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    Physics and chemistry of minerals 26 (1999), S. 206-211 
    ISSN: 1432-2021
    Keywords: Key words Iron ; Fe ; Si alloy ; X-ray diffraction ; Equation of state ; Thermoelasticity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  We have carried out an in situ synchrotron X-ray diffraction study on iron and an iron-silicon alloy Fe0.91Si0.09 at simultaneously high pressure and temperature. Unit-cell volumes, measured up to 8.9 GPa and 773 K on the bcc phases of iron and Fe0.91Si0.09, are analyzed using the Birch-Murnaghan equation of state and thermal pressure approach of Anderson. Equation of state parameters on iron are found to be in agreement with results of previous studies. For both iron and Fe0.91Si0.09, thermal pressures show strong dependence on volume; the (∂KT/∂T)V values are considerably larger than those previously reported for other solids. The present results, in combination with our previous results on ɛ-FeSi, suggest a small dependency of the room-temperature bulk modulus upon the silicon content, less than 0.3 GPa for 1 wt.% silicon. We also find that substitution of silicon in iron would not appreciably change the thermoelastic properties of iron-rich Fe−Si alloys. If this behavior persists over large pressure and temperature ranges, the relative density contrast between iron and iron-rich Fe−Si alloys at conditions of the outer core of the Earth could be close to that measured at ambient conditions, i.e., 0.6% for 1 wt.% Si.
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  • 18
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    Physics and chemistry of minerals 26 (1999), S. 644-648 
    ISSN: 1432-2021
    Keywords: Key words MnO ; CdO ; rock-salt monoxides ; X-ray diffraction ; equation of state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Room-temperature volume measurements up to 8.1 GPa reveal that rock-salt structured MnO and CdO have identical compressibility in the pressure range studied. In the plot of bulk modulus vs unit-cell volume, CdO plots well above the trend of the 3d transition metal monoxides, a behavior that deviates from empirical predictions of constant K 0 V 0. The present observations are in favor of our earlier suggestion that, for isostructural solids, the empirically predicted bulk modulus-volume relationship may be limited to their subsets that share the same valence electron character (i.e., s vs 3d vs 4d). For cations forming transition metal monoxides, variations of Pauling electronegativity with ionic radius show differences that are qualitatively similar to the observed trends of bulk modulus, suggesting that bond covalency differences may contribute to the different behaviors between the 3d and 4d transition metal monoxides.
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  • 19
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    Journal of thermal analysis and calorimetry 39 (1993), S. 197-205 
    ISSN: 1572-8943
    Keywords: derivatograph ; IR spectroscopy ; montmorillonite ; pillared layer clays ; X-ray diffraction ; X-ray fluorescence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Natürliche Montmorillonite wurden durch verschiedene Polyhydroxy-Kationen gestützt. Die resultierenden gestützten Schichttonmaterialien (PILC) wurden mittels Röntgenfluoreszenz, Röntgendiffraktion und IR-Spektroskopie charakterisiert. Mittels einer Kombination von Röntgendiffraktion, Derivatographie und IR-Spektroskopie wurde das thermische Verhalten von Al-PILC im Detail beschrieben und ein Vergleich zu natürlichem Montmorillonit angestellt. Man fand, daß die Thermostabilität von Al-PILC geringer ist, als die von natürlichem Montmorillonit. Unabhängig davon hat eine Hitzebehandlung in der Stabilitätsregion ein signifikantes Sintern von natürlichem Montmorillonit zur Folge, während der Zwischenschichtabstand von Al-PILC stark beeinflußt wird.
    Notes: Abstract Natural montmorillonite was pillared by various polyhydroxy cations. The resulting pillared layer clays (PILCs) were characterized by X-ray fluorescence, X-ray diffraction (XRD) and infrared (IR) spectroscopies. The thermal behaviour of Al-PILC was investigated in detail by a combonation of XRD, derivatography IR spectroscopy and a comparison to natural montmorillonite is given. It was found that thermal stability of Al-PILC is lower than that of natural montmorillonite. However, heat treatment in the stability region results in significant sintering of natural montmorillonite, while the interlayer spacing of Al-PILC is hardly affected.
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  • 20
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    Journal of thermal analysis and calorimetry 57 (1999), S. 559-567 
    ISSN: 1572-8943
    Keywords: calciumsulphate hemihydrate ; differential thermal analysis ; hydrothermal treatment ; infrared analysis ; selenite ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Selenite was boiled in KCl solutions of different concentrations at the respective boiling temperatures and atmospheric pressure. The products were subjected to X-ray diffraction analysis, qualitative infrared analysis, differential thermal analysis and microscopic examination. The product obtained in 1.0 M KCl solution was the β-form of calcium sulphate hemihydrate (α-CaSO4·0.5H2O). In more concentrated KCl solution (1.5, 2.0, 2.5, 3.0, 3.5 or 4.0 M), the α-form of calcium sulphate hemihydrate (α-CaSO4·0.5H2O) was formed, and a reaction took place between KCl and CaSO4, which gave a double salt: potassium pentacalcium sulphate monohydrate (K2SO4·5CaSO4·H2O).
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  • 21
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    Journal of thermal analysis and calorimetry 57 (1999), S. 631-642 
    ISSN: 1572-8943
    Keywords: DSC ; fluorocarbon chain ; polymerizability ; polymorphic behaviors ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The molecular aggregation of acrylic and methacrylic acid esters containing long-fluorocarbon chains: 2-(perfluoroalkyl)ethyl acrylate (FFnEA) and 2-(perfluoroalkyl)ethyl methacrylate (FFnEMA) (F(CF2)nCH2CH2OCOC(X)=CH2, where X=H, CH3 and n=6, 8, 10) was investigated by differential scanning calorimetry (DSC) and temperature controlled X-ray powder diffraction measurement. These compounds exhibited some characteristic polymorphic behaviors depending on the length of fluorocarbon chain and the α-position methyl group. The solid-state polymerization by γ-ray irradiation was studied for these compounds in the various crystal forms. In the solid-state polymerization, highest polymerizability was observed in the crystal form that exists in the highest temperature region for each compound.
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  • 22
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    Journal of thermal analysis and calorimetry 58 (1999), S. 363-368 
    ISSN: 1572-8943
    Keywords: DSC ; lipid ; phase behaviour ; synchrotron radiation ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The phase behaviour and phase stability of lipids are of importance in an understanding of the biological functions of cell membranes. Among a variety of physical techniques employed to study the phase behaviour and structural properties of polar lipids, differential scanning calorimetry and X-ray diffraction have proved to be successful and are the most frequently used methods. Applications involving a combination of the two techniques, particularly when synchrotron radiation is used as the light source of X-ray diffraction, are reviewed in this article.
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  • 23
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    Journal of thermal analysis and calorimetry 56 (1999), S. 429-435 
    ISSN: 1572-8943
    Keywords: DSC ; nickel sulphide ; TG ; toughened glass ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Nickel sulphide (NiS) was characterised using X-ray diffraction, thermal gravimetric analysis (TG) and differential scanning calorimetry (DSC). The 'as received' Millerite, stoichiometric NiS, observed to be slightly nickel deficient, was found to readily decompose in a nitrogen atmosphere at elevated temperatures (450°C max.) to the sulphur deficient Godlevskite, Ni7S6. DSC and X-ray measurements demonstrated that the high temperature form of the Godlevskite was readily stabilised at room temperature. The kinetics of the α-β re-transformation in Godlevskite were then investigated using DSC and were observed to be first order.
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  • 24
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    Journal of thermal analysis and calorimetry 57 (1999), S. 875-881 
    ISSN: 1572-8943
    Keywords: charge transfer ; Kelvin probe ; oxidation ; work function ; zirconia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The extent of the surface charge, that develops during oxidation of zirconia, is determined using work function measurements for both bulk specimen and thin films. The bulk specimen of yttria-doped zirconia (10 mol%) exhibits maxima of the surface electrical effect at 373 and 973 K (130 and 280 mV, respectively) that can be considered in terms of oxygen chemisorption and oxygen non-stoichiometry. Thin film of undoped zirconia exhibits a maximum at 473 K (260 eV). Addition of yttria (10 mol%) to the thin film results in a substantial reduction of the maximum, to about 140 eV, that is shifted up to 600 K.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 473-486 
    ISSN: 1572-8943
    Keywords: cumene ; oxidation ; polymerization ; quinone-amine inhibitors ; solution microcalorimetry ; styrene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of solution microcalorimetry was demonstrated on two model examples – inhibited oxidation of cumene and radical polymerization of styrene. From the experimental dependences of the rate of heat release on time, the rate constants k 7 of the interaction of an inhibitor with radicals of substrate (RO 2 . or R.) in oxidation or in polymerization were determined for the set of inhibitors of N-aryl N-(2-quinone) amine series. It was shown that these compounds are weak inhibitors of oxidation of cumene and rather efficient inhibitor of polymerization of styrene.
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    Plasma chemistry and plasma processing 19 (1999), S. 131-151 
    ISSN: 1572-8986
    Keywords: Styrene ; oxidation ; silent discharge ; plasma ; dielectric barrier
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract A silent discharge plasma reactor has been developed to study the oxidation of styrene vapor in argon/oxygen mixtures. A number of analytical techniques were employed to determine the destruction efficiency and to characterize the intermediate products. The destruction efficiency was measured as a function of initial styrene concentration, temperature, and energy density of the plasma. The formation of solid products was observed in most experiments. At low temperature (100°C), the solid deposit was polymeric in nature, while at high temperature (300°C) the solid appeared to be amorphous carbon. A combination of high temperature and high energy density resulted in high destruction efficiency and minimal production of solid films. The destruction efficiency vs. energy density is shown to be more complex than a simple model predicting exponential behavior. Several reasons for the discrepancy are suggested. The “e-folding” energy density for the destruction of styrene is compared to literature values for other organic compounds, measured using similar types of plasma reactors.
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    Plasma chemistry and plasma processing 19 (1999), S. 383-394 
    ISSN: 1572-8986
    Keywords: Nonthermal plasma ; benzene ; Al2O3 ; BaTiO3 ; oxidation ; absorption ; atmospheric pressure
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The combination of plasma discharge and adsorption was examined for oxidation of dilute benzene in air in a plasma reactor packed with a mixture of BaTiO 3 pellets and porous Al 2 O 3 pellets (i.e., an alumina hybrid reactor). The oxidative decomposition of benzene was enhanced by the benzene concentrating on the Al 2 O 3 pellets. Furthermore, there was a higher selectivity to CO 2 in the products from the hybrid than from a plasma reactor packed with BaTiO 3 pellets alone. The presence of the Al 2 O 3 pellets suppressed the formation of N 2 O.
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    Plasma chemistry and plasma processing 19 (1999), S. 421-443 
    ISSN: 1572-8986
    Keywords: Streamer corona ; NO x removal ; nonthermal plasma ; oxidation ; reduction
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract In this paper, the NO-to-NO 2 conversion in various gaseous mixtures is experimentally investigated. Streamer coronas are produced with a dc-superimposed high-frequency ac power supply (10–60 kHz). According to NO x removal experiments in N 2 +NO x and N 2 +O 2 +NO x gaseous mixtures, it is supposed that the reverse reaction NO 2 +O→NO+O 2 may not only limit NO 2 production in N 2 +NO x mixtures, but also increase the energy cost for NO removal. Oxygen could significantly suppress reduction reactions and enhance oxidation processes. The reduction reactions, such as N+NO→N 2 +O, induce negligible NO removal provided the O 2 concentration is larger than 3.6%. With adding H 2 O into the reactor, the produced NO 2 per unit removed NO can be significantly reduced due to NO 2 oxidation. NH 3 injection could also significantly decrease the produced NO 2 via NH and NH 2 - related reduction reactions. Almost 100% of NO 2 can be removed in gaseous mixtures of N 2 +O 2 +H 2 O+NO 2 with negligible NO production.
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    Molecular and cellular biochemistry 194 (1999), S. 257-263 
    ISSN: 1573-4919
    Keywords: glycation ; oxidation ; collagen ; diabetes ; free radicals
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The present investigation was carried out to understand the effect of metal catalyzed oxidation on glycation and crosslinking of collagen. Tail tendons obtained from rats weighing 200-225 g were incubated with glucose (250 mM) and increasing concentrations of copper ions (5, 25, 50 and 100 μM) under physiological conditions of temperature and pH. Early glycation, crosslinking and late glycation (fluorescence) of collagen samples were analyzed periodically. Early glycation was estimated by phenol sulfuric acid method, and the crosslinking was assessed by pepsin and cyanogen bromide digestion. A concentrationdependent effect of metal ions on the rate of glycation and crosslinking of collagen was observed. Tendon collagen incubated with glucose and 100 μM copper ions showed 80% reduction in pepsin digestion within seven days, indicating extensive crosslinking, whereas collagen incubated with glucose alone for the same period showed only 7% reduction. The presence of metal ions in the incubation medium accelerated the development of Maillard reaction fluorescence on collagen, and the increase was dependent on the concentration of metal ions used. The metal chelator Diethylene triamine penta-acetate significantly prevented the increase in collagen crosslinking by glucose and copper ions. Free radical scavengers benzoate and mannitol effectively prevented the increased crosslinking and browning of collagen by glucose. The results indicate that the metal catalyzed oxidation reactions play a major role in the crosslinking of collagen by glucose. It is also suggested that the prevention of increased oxidative stress in diabetes may prevent the accelerated advanced glycation and crosslinking of collagen.
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    Journal of nondestructive evaluation 12 (1993), S. 3-11 
    ISSN: 1573-4862
    Keywords: Texture ; anisotropic properties ; series expansion ; on-line measurement ; X-ray diffraction ; ultrasound
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    Topics: Electrical Engineering, Measurement and Control Technology , Mathematics
    Notes: Abstract Macroscopic properties of polycrystalline materials may strongly depend on crystal orientation distribution, i.e., the texture of the material. This applies to all kinds of crystallographically anisotropic volume and boundary properties. The necessary texture parameters can be determined from a low number of intensity values measured with a fixed-angle, X-ray texture analyzer which is particularly suited for on-line determination. Alternatively, the texture-property relationship can be used to calculate the texture parameters from property measurement in different sample direction. On-line measurement of the texture can also be used as an indicator for other materials properties such as recrystallization or fatigue.
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  • 31
    ISSN: 1573-4862
    Keywords: Ultrasonic velocity ; X-ray diffraction ; texture components ; elastic anisotropy
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    Topics: Electrical Engineering, Measurement and Control Technology , Mathematics
    Notes: Abstract Effect of processing parameters including cold work and grain size on texture development in copper and 68:32 α-brass thin sheets is investigated. The preferred orientation of grains (texture) is represented quantitatively by the orientation distribution function (ODF) as derived either by X-ray diffraction or by ultrasonic velocity measurements. The texture-induced elastic moduli are derived in the sheet plane at various orientations to the rolling direction. The predicted values of elastic moduli are compared with the mechanically measured ones. An attempt is made to empirically correlate ODF coefficients to the mechanically measured elastic modulus and plastic strain ratio (r-value). The sources of discrepancies such as the limitations of the measuring techniques and the models applied are discussed.
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    Journal of nondestructive evaluation 12 (1993), S. 97-107 
    ISSN: 1573-4862
    Keywords: Plastic strain ratio ; texture ; orientation distribution function ; X-ray diffraction
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    Topics: Electrical Engineering, Measurement and Control Technology , Mathematics
    Notes: Abstract The on-line prediction of metal sheet formability requires that both material characterization (texture identification) and yield loci predetermination be done in very shor time intervals. Of two applicable approaches, i.e., continuum mechanics and crystallography-based methods, only the latter are suitable for this purpose. Several models of plasticity of a polycrystalline material were reviewed, and their applicability to the prediction of plastic anisotropy of face-centered cubic (FCC) metals was evaluated. A tailored set of cold-rolled copper alloy samples was designed and manufactured, representing the wide spectrum of textures and cold work levels typical for the sheet metal industry. The texture was quantitatively described in the form of the orientation distribution functions derived by the inversion of four incomplete pole figures. The Taylor-Bishop-Hill model was applied in order to calculate the planar variation of the plastic strain ratio. The continuum mechanics of textured polycrystals approach was also used for the prediction of the plastic strain-rate ratio for the same set of deformed materials. The theoretical predictions were compared with the plastic strain ratios measured in tensile tests using strain gauges. The applicability of the models for prediction of the plastic anisotropy of FCC metals was discussed in view of the operating deformation mechanisms and other factors such as strain hardening sensitivity and grain size/shape effects.
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    Molecular and cellular biochemistry 200 (1999), S. 103-109 
    ISSN: 1573-4919
    Keywords: sugar cataract ; dulcitol ; glycation ; oxidation ; pyruvate ; ethyl pyruvate ; attenuation effects
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Studies describe an attenuation of sugar cataract formation by topical administration of ethyl pyruvate. Cataract formation was induced by feeding young rats a 30% galactose diet. Mature cataracts appeared in about thirty days. Instillation of the eye drops containing 5% ethyl pyruvate decelerated the process significantly. Biochemically, the effect was reflected by lowering in the contents of dulcitol and glycated proteins. The ATP levels were also higher in comparison to the placebo treated group. The effects are hence attributable to the effect of pyruvate in inhibiting dulcitol synthesis and protein glycation, in addition to its antioxidant properties and metabolic support. The use of esterified pyruvate instead of the unesterified pyruvate was preferred because of its greater penetration through the cornea and consequently a higher concentration attained in the aqueous humor.
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  • 34
    ISSN: 1572-9028
    Keywords: ellipsometry ; carbon monoxide ; methane ; palladium ; palladium oxide ; oxidation ; oscillations ; catalyst
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Spectroscopic ellipsometry is used to monitor the surface of a thick Pd‐film catalyst during the oxidation of either carbon monoxide or methane. Dense PdO layers form under sufficiently lean conditions (excess oxygen) for both reactions. A stable metal surface exists in the case of CO, but a very porous PdO layer develops in the case of methane, under rich conditions. There is a large hysteresis in the conditions for PdO formation in the case of CO oxidation. Spontaneous oscillations in catalytic activity and Pd‐surface composition occur for both reactions, the higher activities corresponding to O‐atom‐rich or PdO‐rich surfaces for CO or methane oxidation, respectively.
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    Topics in catalysis 8 (1999), S. 45-55 
    ISSN: 1572-9028
    Keywords: Raman spectroscopy ; surface‐enhanced Raman spectroscopy ; oxidation ; synergy effects ; oxygen exchange ; oxidative coupling of methane ; nitric oxide decomposition ; methanol oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Advantages and limitations of laser Raman spectroscopy (LRS) as an in situ vibrational spectroscopy for the study of catalytic materials and surfaces under working conditions are discussed. Measurements can be carried out at temperatures as high as 1200 K in controlled atmospheres. Modern instrumentation permits time resolutions in the sub‐second regime for materials with high Raman cross sections. Transient studies are thus possible. Several examples are presented of in situ LRS studies including the phase analysis of bismuth molybdate and VPO oxidation catalysts, synergy effects and oxygen exchange in Sb2O3/MoO3 oxide mixtures, intermediates in oxidative coupling of methane, NO decomposition on Ba/MgO catalysts, and transient SERS studies of partial oxidation of methanol on Ag single crystal surfaces and of the reduction of oxide overlayers on electrodeposited Rh layers.
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    Journal of sol gel science and technology 14 (1999), S. 75-86 
    ISSN: 1573-4846
    Keywords: silicon oxycarbide ; BlackglasTM ; ceramic matrix composites ; 29Si NMR ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract BlackglasTM polysiloxane systems produce silicon oxycarbide glasses by pyrolysis in inert atmosphere. The silicon oxycarbides evidence oxidative degradation that limits their lifetime as composite matrices. The present study characterizes bonding rearrangements in the oxycarbide network accompanying increases in pyrolysis temperature. It also addresses the changes in susceptibility to oxidation due to variations in the distribution of Si bonded species obtained under different processing conditions. The study is carried out using 29Si nuclear magnetic resonance (NMR) spectroscopy and a design of experiments approach to model the oxidation behavior. The NMR results are compared with those obtained by thermogravimetric analysis (TGA). Samples pyrolyzed under inert conditions are compared to those pyrolyzed in reactive ammonia environments.
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    Journal of sol gel science and technology 14 (1999), S. 49-68 
    ISSN: 1573-4846
    Keywords: silicon oxycarbide ; oxidation ; silsesquioxane ; preceramic
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We have undertaken a systematic study of the oxidation chemistry for a range of SiOC ceramics derived from silsesquioxane polymeric precursors. This study examines the oxidation for 500 hours at 600, 800, 1000 and 1200°C for four SiOC powders. The material changes upon oxidation were characterized qualitatively by color change and optical microscopy and quantitatively by weight and composition change. In this study we employ a very easy method that uses the weight change upon oxidation and a carbon analysis after oxidation to arrive at the composition of the oxidized SiOC. Combined these qualitative and quantitative techniques have shown that on oxidation at 800 and 600°C the SiOC composition is more rapidly changed to that of silica than oxidation over the same time frame at 1000 or 1200°C. The data indicates that this difference is due to the relative rates of oxidation of the excess carbon versus the Si—C bonds in the SiOC. At lower temperatures initially the carbon oxidation predominates which leads to higher porosity throughout the material and an increase in the surface area with eventually ‘complete’ oxidation to silica. At higher temperatures the Si—C bond oxidation rate is comparable to the rate of oxidation of carbon. This allows a silica-like surface to build up on the SiOC, which slows all subsequent reactions due to the necessity to diffuse O2 in and COx out of the bulk. Under these oxidation conditions materials that originally contain high amounts of excess carbon are more quickly oxidized to silica than those that contain minimal amounts of excess carbon, as confirmed by elemental analysis and optical microscopy. Regardless of the time or temperature of the oxidation conditions no materials were found to be completely stable to oxidation. SiOC materials with low levels of excess carbon showed the best resistance to change upon oxidation.
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    Physics and chemistry of minerals 26 (1999), S. 257-263 
    ISSN: 1432-2021
    Keywords: Key words Acetamide ; DRIFT spectroscopy ; Intercalation ; Hydrogen bonding ; Kaolinite ; Raman spectroscopy ; X-ray diffraction
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    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  Upon intercalation of both ordered (low defect) and disordered (high defect) kaolinites with acetamide, two types of interaction are observed. Firstly, hydrogen bonding between the NH2 groups of the acetamide with the siloxane oxygens is formed, as evidenced by the formation of two new bands at 3400 and 3509 cm–1. Secondly, the appearance of additional bands at ∼3600 cm–1 in both the infrared and Raman spectra of the acetamide intercalates is attributed to a second type of hydrogen bonding by the interaction of the C=O group and the inner surface hydroxyls. Changes in the intensity of the hydroxyl deformation modes in the 895 to 940 cm–1 region are attributed to the changes in the hydrogen bonding of the kaolinite surfaces. It is proposed that the hydrogen bonding between the adjacent kaolinite layers is replaced with hydrogen bonding between both kaolinite surfaces and the acetamide molecule. Changes in the molecular structure of acetamide are observed upon intercalation. The amide 1 band is lost and replaced with a well-defined NH2 deformation vibration. The loss of the amide 1 band is attributed the hydrogen bond formation between the amide hydrogens and the siloxane surface. The bands of the C=O group at 1680 and 1740 cm–1 become a single band at 1680 cm–1. The amide 2 band remains unchanged. The lack of intensity of the 1740 cm–1 band is attributed to the formation of hydrogen bonding between the inner surface hydroxyl groups and the carbonyl group.
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    Physics and chemistry of minerals 26 (1999), S. 406-414 
    ISSN: 1432-2021
    Keywords: Key words Lawsonite ; Equation of state ; X-ray diffraction ; High-pressure ; High-temperature
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    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  A pressure-volume-temperature data set has been obtained for lawsonite [CaAl2Si2O7(OH)2.H2O], using synchrotron X-ray diffraction and an externally heated diamond anvil cell. Unit-cell volumes were measured to 9.4 GPa and 767 K by angle dispersive X-ray diffraction using imaging plates. Phase changes were not observed within this pressure-temperature range, and lawsonite compressed almost isotropically at constant temperature. The P-V-T data have been analyzed using a Birch- Murnaghan equation of state and a linear equation of state expressed as β=–1/V0 (∂V/∂P) T . At room temperature, the derived equation of state parameters are: K 0=124.1 (18) GPa K'0 set to 4) and β–1=142.0(24) GPa, respectively. Our results are intermediate between previously reported measurements. The high-temperature data show that the incompressibility of lawsonite decreases with increasing temperature to ∼500 K and then increases above. Hence, the second order temperature derivative of the bulk modulus is taken into account in the equation of state; a fit of the volume data yields K 0=123.9(18) GPa, (∂K/∂T)P=–0.111(3) GPa K–1, (∂2 K/∂T 2)P=0.28(6) 10–3 GPa K–2, α0=3.1(2) 10–5 K–1, assuming K'0=4.
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    Physics and chemistry of minerals 26 (1999), S. 419-424 
    ISSN: 1432-2021
    Keywords: Key words Iron ; Fe-Si alloys ; X-ray diffraction ; Phase transformation
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    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract In situ X-ray diffraction experiments at high pressure were carried out up to 8.9 GPa and 1100 °C to study phase transformations of iron and two iron-silicon alloys Fe0.91Si0.09 and Fe0.83Si0.17. For iron, the transformation from the bcc phase to the fcc phase was observed at pressures 3.8–8.2 GPa and temperatures that are consistent with previous in situ X-ray diffraction studies. Reversal of the transformation of iron was found to be sensitive to temperature; hysteresis of the transformation increased from 25 °C at 3.8 GPa to 100 °C at 7.0 GPa, primarily because the bcc-fcc phase boundary has a negative Clayperon slope. In the binary system Fe-Si, the observations of the present study indicate that the ferrite (bcc phase)-stabilizing behavior of silicon persists at high pressures and that the maximum solubility of silicon in the fcc phase increases with increasing pressure: (1) the transformation from the bcc phase to the fcc phase was observed in Fe0.91Si0.09 at 6.0, 7.4 and 8.9 GPa and the temperatures measured at the onset of the transformations were 300 °C higher than those in iron at similar pressures, (2) the transformation rate in Fe0.91Si0.09 was extremely sluggish compared to that of iron, and (3) the bcc-fcc phase transformation was not observed in Fe0.91Si0.09 at 4.7 GPa up to 1000 °C and in Fe0.83Si0.17 at 8.2 GPa and 1100 °C.
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    Physics and chemistry of minerals 26 (1999), S. 506-512 
    ISSN: 1432-2021
    Keywords: Key words Anapaite ; Mössbauer spectroscopy ; oxidation
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    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Mössbauer spectra (MS) of anapaite (Ca2 Fe2+(PO4)2 · 4H2O) and of a sample after being immersed in a 4% H2O2 solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420 K and 11 to 300 K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe2+ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370 K ± 25 K and 340 K ± 25 K, and the intrinsic isomer shifts as 1.427 ± 0.005 mm/s and 1.418 ± 0.005 mm/s respectively. From the external-field (60 kOe) MS recorded at 4.2 and 189 K for the non-treated sample, the principal component V zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η ≈ 0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE Q(T), cannot be interpreted on the basis of the thermal population of the 5 D electronic levels resulting from the tetragonal compression of the O6 co-ordination. The low-temperature linear behaviour of ΔE Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2 K produces magnetic hyperfine splitting with effective hyperfine fields of −136, −254 and −171 kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H2O2 concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe2+ (∼6.5%) is converted into Fe3+.
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  • 42
    ISSN: 1432-2021
    Keywords: Key words Majorite garnet ; X-ray diffraction ; PVT observation
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    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The high-pressure and temperature equation of state of majorite solid solution, Mj0.8Py0.2, was determined up to 23 GPa and 773 K with energy-dispersive synchrotron X-ray diffraction at high pressure and high temperature using the single- and double-stage configurations of the multianvil apparatuses, MAX80 and 90. The X-ray diffraction data of the majorite sample were analyzed using the WPPD (whole-powder-pattern decomposition) method to obtain the lattice parameters. A least-squares fitting using the third-order Birch-Murnaghan equation of state yields the isothermal bulk modulus, K T0  = 156 GPa, its pressure derivative, K′ = 4.4(±0.3), and temperature derivative (∂K T /∂T) P = −1.9(±0.3)× 10−2 GPa/K, assuming that the thermal expansion coefficient is similar to that of pyrope-almandine solid solution.
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  • 43
    ISSN: 1573-9171
    Keywords: iron(II) and ruthenium(II) complexes ; synthesis ; carbonyl, cyclopentadienyl, benzoate ligands ; crystal structure ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Complexes of Fe(II) and Ru(II) of the general formula Cp(OC)2MOC(O)C6H4X-p, where M=Fe, X=H, F (1, 2) or M=Ru, X=H, F (3, 4) have been prepared by reactingp-XC6H4COOAg with [CpFe(CO)2]2 or CpRu(CO)2I. The crystal structures of complexes1–3 have been determined using X-ray diffraction. Compounds1 and3 are isomorphous. The COO group in1–3 is coordinated as a monodentate ligand. As the latter and the CO ligands are electronically non-equivalent, the coordination of the Cp ligand to the metal is slightly asymmetric.
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    Russian chemical bulletin 42 (1993), S. 55-59 
    ISSN: 1573-9171
    Keywords: alkanes ; oxidation ; homogeneous catalysis ; hydrogen peroxide ; vanadium ; hydroxyl radicals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Alkanes (cyclohexane, hexane, heptane isomers) are effectively oxidized in CH3CN at 20–70°C by hydrogen peroxide when catalyzed by a Bu4NVO3-pyrazine-2-carboxylic acid system. Alkyl hydroperoxide is the main product; an alcohol and a ketone or an aldehyde are also formed. Under these conditions benzene is oxidized to give phenol, while alkyl benzenes yield oxygenation products both of the ring and the side chain. It has been assumed that the interaction of H2O2 with VO3 − gives rise to generation of HO radicals and other radical-like vanadium containing species that abstract a hydrogen atom from an alkane, RH. The radical R. formed reacts with O2 to produce ROO. which is then transformed to alkyl hydroperoxide.
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  • 45
    ISSN: 1573-9171
    Keywords: bromination ; oxidation ; N-(7-methyl-5-oxo-5H-1,3,4-thiadiazolo[3,2-a]pyrimidin-2-yl)-N-phenylhydrazine ; azo-derivatives
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Synthesis of the title compound is described and its reaction with bromine is studied. This involves oxidation of the hydrazine moiety and sequential bromination of the benzene and thiadiazolopyrimidine nuclei to give, respectively, 2-(4-bromophenylazo)-7-methyl-5-oxo-5H-1, 3,4-thiadiazolo[3,2-a]pyrimidine and 6-bromo-2-(4-bromophenylazo)-7-methyl-5-oxo-5H-1, 3,4-thiadiazolo[3,2-a]pyrimidine.
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  • 46
    ISSN: 1573-9171
    Keywords: alkylurea nitroxides ; oxidation ; alkylureidooxoammonium salts ; nitrosation ; alkylnitrosoureidooxoammonium salts ; water-soluble alkylnitrosoureas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 4-(3-Alkylureido)-2, 2, 6, 6-tetramethylpiperidine-1-oxyls are rapidly oxidized by N2O4 or NOCl to 4-(3-alkylureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium nitrates and chlorides, which are then nitrosated to 4-(3-alkyl-3-nitrosoureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium salts. The perchlorates of the latter were prepared by an exchange reaction with HClO4. The nitrosation of alkylureidooxoammonium salts is the first example of chemical modification of oxoammonium derivatives in which the highly reactive 〉N+=O group is inert toward the reagent.
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    Russian chemical bulletin 42 (1993), S. 1027-1031 
    ISSN: 1573-9171
    Keywords: nitroxyls ; hydrazobenzene ; reduction ; tetranitromethane ; oxidation ; kinetics ; constants ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The values of isotropic HFS constantsa N were obtained for nitroxyl radicals (NR) of the piperidine series in hexane and water. The interrelation between rate constants for NR reduction and oxidation reactions, isotropic HFS constantsa N, inductive constants σ″ of the piperidine substituents, and electrochemical characteristics of NR were found. The dependence of the rate constants for the reduction of NR by hydrazobenzene (HB) and its oxidation by tetranitromethane (TNM) upon the Hammett type inductive constantsσ EPR, obtained using HFS constantsa N as the basis, was analyzed. The solvent effect on the reduction and oxidation reaction rate constants, the kinetic isotopic effect of the reduction reaction for a number of NR-HB systems, and alternative reaction mechanisms are considered.
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    Russian chemical bulletin 42 (1993), S. 365-370 
    ISSN: 1573-9171
    Keywords: 17α-pregnanes ; X-ray diffraction ; reactivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The structure of the title compound (1) has been studied by means of X-ray diffraction. The region of cycleD in epoxide1 was compared with that of the 16,17α-epoxy derivatives of progesterone and pregnenolone (studied previously) as well as with that of the respective 16,17α- and 16,17β-cyclopropano analogs. In contrast to the 16,17α-epoxy-20-oxo derivatives, in compound1 the electron conjugation of the epoxide ring with the CH3CO group at C(17) is partly disrupted. Moreover, the steric congestion at C(17) is significantly less pronounced in 16,17β-epoxide1 than in its 16,17α-counterpart. Both of these factors, especially steric decongestion, are favorable for nucleophilic attack at C(17) in the molecule of1. The X-ray diffraction data do not contradict the previously advanced mechanism of epoxide ring opening in 16,17α- and 16,17β-epoxy-20-oxo steroids by nucleophilic reagents.
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  • 49
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    Russian chemical bulletin 42 (1993), S. 1955-1959 
    ISSN: 1573-9171
    Keywords: triphenylbismuth diacylates ; oxidation ; phenylation ; alcohols ; diols ; enols ; phenols ; amines ; aminoesters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Triphenylbismuth diacylates, Ph3Bi(O2CR)2 (R = Me, Et, Ph, CF3, CH=CH2), are novel effective reagents for fine organic synthesis. They oxidize primary and secondary alcohols and di-tert-glycols under mild conditions to form the corresponding carbonyl compounds in high yields;O- andN-phenylate alcohols, enols, and amines; andO- ando-C-phenylate phenols.
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  • 50
    ISSN: 1573-9171
    Keywords: triphenyl-N-(6-methylpyridyl-2)phosphinimine ; iminophosphoranes, complexes with copper(II) ; X-ray diffraction ; ESR data
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The complex of copper(II) dichloride with triphenyl-N-(6-methylpyridyl-2)phosphinimine has been studied by X-ray diffraction. This compound has a dimeric structure with two μ2-bridge chlorine atoms. The coordination of copper atoms by three chlorine atoms and the N atom of the heterocycle is of a strongly distorted planar-square type. A peculiar feature of this structure is the presence of intramolecular contacts Cu...N (2.504 Å and 2.492 Å) involving the imine nitrogens of the P,N-containing ligands which are responsible for strong additional coordination of the copper atoms. In methanol the P,N-containing ligand forms a complex with Cu(II) where the metal-to-ligand ratio is equal to 1∶2. The ESR data point to the bidentate nature of the ligand in solution, where all four nitrogen atoms, contributed by both of the ligands, are located in the plane of the metal atom.
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  • 51
    ISSN: 1572-8978
    Keywords: Plasma polymers ; oxidation ; XPS ; photoelectron binding energy
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The incorporation of oxygen into nitrogen-containing plasma deposited polymers was studied by X-ray Photoelectron Spectroscopy (XPS). As the oxygen content of the plasma polymer increased, the binding energy of the N 1s photoelectrons increased. Conversely, the binding energy of the O 1s photoelectrons was inversely proportional to the nitrogen content of the plasma polymer. The data from a large number of samples all obeyed the same “universal” correlations of photoelectron binding energy versus chemical composition. The data were described by the same curve regardless of whether the oxygen was incorporated rapidly into the thin film during plasma deposition or whether the oxygen was added slowly during spontaneous oxidation of the film in air. This implies that the same thermodynamic principles of radical reactions governed the addition of oxygen to the plasma polymer. The shift in the O 1s and N 1s photoelectron binding energies as a function of chemical composition was used to monitor the proximity of nitrogen and oxygen. By contrasting the experimental data with a simple binomial model which described the random addition of oxygen to a lattice containing carbon and nitrogen, we were able to show that oxygen was preferentially added near nitrogen-containing groups in plasma polymers.
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  • 52
    ISSN: 1573-904X
    Keywords: anti-HIV drugs ; thiocarbamate ; emulsion ; solubilization ; stabilization ; disulfide exchange ; oxidation ; parenteral formulation ; AIDS chemotherapy ; Uniroyal Jr
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The O-alkyl-N-aryl thiocarbamate, I, (2-chloro-5-[[(l-methyl-ethoxy)thioxomethyl]amino]benzoic acid, 1-methylethylester, NSC 629243, also known as Uniroyal Jr.) is an experimental anti-HIV drug with very low water solubility (1.5 µg/mL). Early clinical studies required an injectable solution at ≈15 mg/mL, representing a solubility increase of ≈104-fold. Adequate solubilization of this hydrophobic drug was achieved in 20% lipid emulsions. Extemporaneous emulsions were prepared by adding a concentrated drug solution to a commercially available parenteral emulsion. Various methods of preparation to minimize drug precipitation during its addition and enhance redissolution of precipitated drug were evaluated. The stability and mechanism(s) of decomposition of NSC 629243 in both 20% lipid emulsions and in natural oil vehicles were examined. In lipid emulsions, the shelf life at 25°C varied from 1 to 〉10 weeks, depending on the extent to which air was excluded from the preparation. The shelf life of 50 mg/mL solutions in natural oils at 25°C varied from 〈1 to 〉100 days depending on the oil and its supplier. A qualitative correlation was found between the initial rate of oxidation and the peroxide concentration in the oil. The primary degradation product in both systems was shown to be a disulfide dimer, II, formed via oxidation. Oxidation was inhibited by vacuum-sealing of emulsion formulations or incorporation of an oil-soluble thiol, thioglycolic acid (TGA), into oil formulations. TGA may inhibit oxidation by consuming free radicals or peroxide initiators or by reacting with the disulfide, II, to regenerate the starting drug.
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  • 53
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    Colloid & polymer science 277 (1999), S. 1220-1223 
    ISSN: 1435-1536
    Keywords: Key words Nonaqueous liquid crystals ; Hexagonal and lamellar phase ; Gel phase ; X-ray diffraction ; Calorimetry ; Phase diagram
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Two mixtures of the binary system K-behenate/glycerol, x KC22 = 0.30 and 0.50 (x = mole fraction), have been investigated as a function of temperature using small- and wide-angle X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The binary phase diagram based on texture observations using polarizing optical microscopy was confirmed. XRD and DSC measurements provided concordant results with respect to the range of the phase regions in the phase diagram. Only differences between the DSC curves for rising and falling temperatures were detected. The recorded XRD and DSC data of the liquid crystals and gel phases observed are also in agreement with previously reported investigations on K-soap/glycerol. The C ⇆ G and G ⇆ Lα phase transitions correlate with a sharp shift in the d value of the first small-angle reflection. The G phase is characterized by a split of the first small-angle reflections. Also, the position and shape of the wide-angle reflections change and the peak intensity is reduced.
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    Journal of inclusion phenomena and macrocyclic chemistry 34 (1999), S. 19-29 
    ISSN: 1573-1111
    Keywords: analgesic ; p-bromoacetanilide ; cyclodextrin ; inclusion complex ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The preparation and X-ray crystal structure of a 1 : 1 complex between β-cyclodextrin (β-CD) and the analgesic p-bromoacetanilide are reported. Thermogravimetric and UV spectrophotometric analyses of single crystals grown from an aqueous solution containing host and guest in 1 : 1 molar ratio yielded the composition β-CD ċ p-bromoacetanilide ċ$ 13.5H2O. Crystals of the complex are triclinic, space group P1, with a = 15.197(3), b = 15.613(2), c = 15.743(4) Å, α = 87.16(2), β = 98.29(2), γ = 103.39(1)° and Z = 2 crystallographically independent complex units per unit cell. The β-CD molecules form head-to-head dimers which pack in the channel-mode. Each dimer contains two guest molecules whose acetylamino substituents are located at the dimer interface while the bromine atoms protrude from the β-CD primary faces. The acetyl residues of both guest molecules were found to be disordered but the X-ray data permitted
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    Journal of chemical ecology 25 (1999), S. 611-628 
    ISSN: 1573-1561
    Keywords: Terrestrial isopods ; Oniscidea ; Porcellio scaber ; phenolics ; hydrolysis ; oxidation ; detoxification ; hindgut cuticle ; gut microbiota ; hepatopancreatic bacteria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract When adults of Porcellio scaber fed on litter prior to an artificial diet containing 5% of commercially available tannic acid, 55% of the ingested galloylglucose esters was excreted unchanged, about 25% was hydrolyzed, and 20% was oxidized during the gut passage. After reducing the counts of microorganisms in the gut of P. scaber, the data obtained indicated an important role of ingested platable microorganisms in hydrolyzing gallotannins. Oxidation of phenolics appeared to be mainly due to the endosymbiotic bacteria of the hepatopancreas. Microbial counts in the hindgut were strongly reduced by ingested galloylglucose esters, while gallic acid in the diet (2%) reduced the number of palatable fungi and bacteria less strikingly, and increased the total number of the gut microbiota. Hepatopancreatic bacteria were only slightly affected by ingested tannic acid, since the hepatopancreas contained only few galloylglucose esters. This may be due to the permeability of the hindgut cuticle: the cuticle of the anterior hindgut was freely permeable to gallic acid, while it was nearly impermeable to larger polyphenols. The cuticle of the posterior hindgut was permeable to only about 4% of the gallic acid present in the hindgut lumen. The results are discussed with respect to potentially harmful effects of ingested hydrolyzable tannins and their digestion in Porcellio scaber.
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  • 56
    ISSN: 1435-1536
    Keywords: Key words Lyotropic liquid crystals ; X-ray diffraction ; Calorimetry ; Gel phase ; K-myristinate
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    Notes: Abstract Samples from the three selected concentrations x KC14 = 0.25,0.37, and 0.50 of the K-myristinate/glycerol (KC14/Gl) binary system have been investigated by means of small- and wide-angle X-ray diffraction measurements as well as differential scanning calorimetry (DSC) measurements as a function of temperature. The results are – The G1 gel phase, contained in the preliminary phase diagram according to Dörfler and Senst [(1993) Colloid Polym Sci 271: 173], is nonexistent. – The same applies of the isotropic phase in the preliminary phase diagram according to Dörfler and Senst. Initially an isotropic or a cubic phase was assumed based on polarized microscopy texture observations. X-ray diffraction and DSC measurements provided no indication for their existence. – Due to the nonexistence of the G1 and isotropic phases the preliminary phase diagram of the KC14/Gl binary system had to be corrected. The region of the lamellar phase extends over a wider region. – X-ray diffraction and DSC measurements provided concordant results, which were further confirmed by electron microscopic investigation. Differences in phase-transition points from DSC data obtained for rising and falling temperatures have been observed. – The crystalline-to-gel phase transition correlates with a sharp shift in the d value of the first small-angle reflex. – The gel phase is accompanied by a distinct splitting of the first small-angle reflexes. The wide-angle reflexes show rearrangement and reduced intensity. – Similar to the crystalline-to-gel phase transition, the gel-to-lamellar phase transition is accompanied by a sharp change in the d values.
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    Colloid & polymer science 277 (1999), S. 340-346 
    ISSN: 1435-1536
    Keywords: Key words Chirality ; Clay organocomplexes ; Intercalation ; Nanophase reactors ; Binary liquid mixtures ; X-ray diffraction
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    Notes: Abstract Chiral phenylethyl alkylammonium montmorillonites were prepared by ion exchange of Na montmorillonite (from Wyoming). The structure of chiral montmorillonite organocomplexes was studied in the dry state by X-ray diffraction, IR spectroscopy and 13C cross-polarized MAS NMR and after swelling by X-ray diffraction. The phenylethylammonium ions are intercalated in montmorillonite in a monolayer structure, while higher derivatives containing alkyl chains with lengths of n c=10−16 take up a bilayer orientation. The hydrophobized clay mineral is readily dispersed in organic solvents, for example in ethanol, toluene and their binary mixtures. Due to selective adsorption, the liquids penetrate into the interlamellar space under significant interlayer expansion producing a great variety of alkyl chain orientations within the interlamellar space, depending on the length of alkyl chains and on the mixture composition. Such interlamellar spaces are possible chiral nanoreactors with adjustable volume and may be prospectively utilized for shape-selective catalytic reactions and the production of enantiomers.
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    Colloid & polymer science 277 (1999), S. 1104-1108 
    ISSN: 1435-1536
    Keywords: Key words Nonaqueous lyotropic liquid crystals ; X-ray diffraction ; Calorimetry ; Gel phase ; K-palmitate ; Phase diagram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Three mole fractions of the binary system K-palmitate/glycerol (KC16/Gl) xKC16 = 0.30, 0.37 and 0.50 have been investigated as a function of temperature by small- and wide-angle X-ray diffraction investigations and differential scanning calorimetry (DSC) measurements. The existence of a gel-like region, named G1 in the preliminary binary phase diagram [4], could not be confirmed. Consequently, a corrected version of the phase diagram of the KC16/Gl system is established. According to this corrected phase diagram at low K-palmitate concentrations, xKC16 〈 0.25, the transitions crystalline phase (C) ⇆ hexagonal phase, chains fluid (Hα) ⇆ isotropic, micellar phase (S) occur with rising temperature. At xKC16 〉 0.25 the transitions C ⇆ gel phase (G) ⇆ lamellar phase, chains fluid (Lα) were observed. X-ray diffraction and DSC measurements provided concordant results. Only differences in the phase transition temperatures from DSC curves obtained at rising and falling temperatures were observed. The phase transitions C ⇆ G, G ⇆ Lα and G ⇆ Hα correlate with a sharp shift in the d value of the first small-angle reflection. The occurrence of the G phase is accompanied by a distinct split of the first small-angle reflections. Simultaneously, the wide-angle reflections change and the peak intensity is reduced.
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    Colloid & polymer science 277 (1999), S. 1109-1114 
    ISSN: 1435-1536
    Keywords: Key words Nonaqueous liquid crystals ; Gel phase ; X-ray diffraction ; Calorimetry ; K-stearate
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The K-stearate/glycerol (KC18/Gl) binary system was studied at mole fractions of stearate of x KC18 = 0.10, 0.25, 0.30 and 0.50. Small- and wide-angle X-ray diffraction (XRD) measurements were combined with differential scanning calorimetry (DSC) measurements at different temperatures. The investigations were intended to verify the previously published phase diagram and were targeted at the confirmation of the gel-like (G1) phase and the isotropic (I) phase. The XRD and DSC measurements lead to the conclusion that the G1 phase as well as the I phase, the existence of which had been proposed from texture observations, do in fact not exist. Consequently, a correction of the preliminary phase diagram is given. This corrected phase diagram reveals the crystalline phase (C) ⇆ gel phase (G) ⇆ hexagonal phase (Hα) ⇆ isotropic, micellar phase phase transitions for low KC18 concentrations of x KC18 = 0.15–0.3 and the C ⇆ G ⇆ lamellar phase (Lα) phase transitions for concentrations about or higher than x KC18 = 0.35. The C, G, Lα and Hα phases have been further characterized by structural parameters (characteristic d values) as a function of temperature. The phase transitions C ⇆ G, G ⇆ Lα and G ⇆ Hα correlate with sharp shifts in the d value of the first small-angle reflections.
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  • 60
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    Journal of thermal analysis and calorimetry 55 (1999), S. 681-690 
    ISSN: 1572-8943
    Keywords: chromia ; Fe-Cr alloy ; gas-solid reaction kinetics ; H2/H2O gas mixtures ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The high-temperature oxidation behavior of a ferritic alloy (SUS 430) in a SOFC environment, corresponding to the anode (H2/H2O gas mixture) and cathode (air) operating conditions, was determined with regard to application of the alloy as a metallic separator material in SOFC. The oxidation kinetics of Fe-16Cr alloy (SUS 430), was studied by thermogravimetry in H2/H2O gas mixtures with pH/pHO=94/6 and 97/3 and in air, in the temperature range 1023-1223 K, for 3.6 up to 1080 ks. It was found that the protective oxide scale, composed mainly of Cr2O3 with uniform thickness and excellent adhesion to the metal substrate, grows in accordance with the parabolic rate law. The dependence of the parabolic rate constant, kp, of the scale on temperature obeys the Arrhenius equation: kp=6.8×10-4 exp (-202.3 kJ mol-1R-1T-1) for H2/H2O gas mixtures with pH/pHO=94/6. The determined kp was independent of the oxygen partial pressure in the range from 5.2×10-22 to 0.21 atm at 1073 K, which means that the rates of growth of the scale on Fe-16Cr alloy in the above-mentioned atmospheres are comparable. The oxidation test results on Fe-16Cr alloy in H2/H2O gas mixtures and air demonstrate the applicability of SUS 430 alloys as a separator for SOFC.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 981-987 
    ISSN: 1572-8943
    Keywords: nickel phosphates ; nickel phosphides ; Ni-P alloys ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DTA in conjuction with X-ray diffraction analysis with a high-temperature camera and infrared spectroscopy was employed to determine the mechanism of oxidation of Ni-P alloys. Amorphous Ni-P powders were obtained from a nickel(II) sulphate bath as a nickel source and sodium dihydrophosphate(I) as a reducing agent. The crystallization product is composed of two phases: (f.c.c.) Ni and (b.c.t.) Ni3P. The amorphous to crystalline transformation takes place in the temperature range 280–330°C. Ni3P samples were heated from room temperature to 1050°C in air atmosphere at 5°C min−1. It was found that the first stage of oxidation of Ni3P goes through the intermediate phase of Ni12P5 formation to Ni2P. Some exothermic reactions were observed. Heating runs were interrupted after each reaction for crystal structure determination by IR spectrometry. Infrared spectra are reported and it is shown that the structure units present in the amorphous products at about 700°C were the oxoanions PO3 − and P2O7 −. The final products of the oxidation process are NiO and Ni3(PO4)2.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 125-130 
    ISSN: 1572-8943
    Keywords: Bi2O3-PbO-CaO system ; DTA ; solid-state reactions ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Following our previous research, this work is dedicated to the study of phase formation in the subsolidus domain of the Bi2O3-PbO-CaO system. Former investigations performed by DTA/TGA and XRD have pointed out that under non-isothermal conditions only the formation of binary compounds occurs. Under such conditions these compounds could be non-equilibrium phases. In order to establish the conditions of formation of equilibrium phases, a study of the Bi2O3-PbO-CaO system, in isothermal conditions, was carried out. The results obtained in isothermal conditions have confirmed the presence of Bi2O3-rich solid solutions and Ca2PbO4 as main equilibrium phases. An attempt to represent the phase relations of the mentioned system at 700°C should be equally mentioned.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 193-202 
    ISSN: 1572-8943
    Keywords: barium strontium fluorohalides ; DTA ; X-ray diffraction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We have studied the solid-liquid equilibrium of the system Sr1−yBayFCl1−xBrx using DTA and X-ray diffraction techniques. The entire composition range in this system yields solid solutions which crystallize in the PbFCl (Matlockite) structure type. The melting points of the entire composition range have been parametrized (within 5°C rms error) using a biquadratic fit of the available data obtained by experiment and from the literature.
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    Journal of superconductivity 12 (1999), S. 609-615 
    ISSN: 1572-9605
    Keywords: Nonisothermal decomposition ; freeze-dried powder ; Bi(Pb)-Sr(Ba)-Ca-Cu-O system ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
    Notes: Abstract Nitrate powder with cation composition Bi:Pb:Sr:Ba:Ca:Cu = 1.8:0.4:1.8:0.2:1.2:2.0 was obtained by spray-frozen, freeze-drying technique. Samples of the nitrate precursor powder were placed in a heated furnace (heating rate ∼100°C/min) and extracted in air when temperature of the powdered samples attained values of 439, 495, 550, 600, 640, 647, 717, 766, 814, and 850°C. Samples have been investigated by X-ray diffraction analysis. The obtained data allow us to propose and discuss phase formation and decomposition processes and reactions that occur in non-isothermal conditions at different temperatures during thermal decomposition of the nitrate powder.
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  • 65
    ISSN: 1588-2837
    Keywords: V2O5−ZrO2 catalyst ; oxidation ; o-xylene ; temperature stability
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    Topics: Chemistry and Pharmacology
    Notes: Abstract It has been established that at high temperatures (above 450°C) the V2O5−ZrO2 catalyst exhibits a higher selectivity in the oxidation ofo-xylene to phthalic anhydride than does the conventional V2O5−TiO2(a) catalyst. The catalyst selectivity is found to increase with respect to partial oxidation ofo-xylene, the valuable by-product maleic anhydride being obtained. Studies by different physicochemical methods have shown that V2O5−ZrO2 undergoes no significant phase and structural changes under high-temperature conditions.
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  • 66
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    Reaction kinetics and catalysis letters 66 (1999), S. 97-104 
    ISSN: 1588-2837
    Keywords: Heterogeneous catalysis ; oxidation ; temperature hysteresis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The temperature hysteresis observed in the oxidation of CO on both supported and unsupported catalysts can be explained by the local overheating of active centers rather than by transitions from one steady state to another.
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  • 67
    ISSN: 1588-2837
    Keywords: Catalyst ; ceramic foam ; molten salt ; Nox ; oxidation ; soot
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Diesel soot is combusted simultaneously by two reactions: combustion with NO2 and combustion with O2 with the aid of a molten salt catalyst. Both reaction pathways should always be considered to avoid misinterpretation of experimental data.
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    Reaction kinetics and catalysis letters 68 (1999), S. 285-289 
    ISSN: 1588-2837
    Keywords: Enthalpy ; chain propagation ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A calculation of the enthalpies of elementary steps of the intra- and intermolecular chain propagation for model oxidation reactions of ethers, esters, ketones and hydrocarbons has been carried out. The heats of the intermolecular and intramolecular transfer of free valence with participation of peroxy radicals and C−H bond of the oxygen-containing compounds are shown to be comparable.
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    Reaction kinetics and catalysis letters 68 (1999), S. 325-330 
    ISSN: 1588-2837
    Keywords: vitrification ; glass structure ; oxidation ; solid phase kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The capture of oxygen molecules by deep traps during oxygen diffusion in butanol glasses has been studied at 77 K as the kinetics of thetert-butyl radical oxidation. Slow glass formation in the samples increases the concentration of deep traps in the matrix. The total value of nonrelaxed free volume has no effect on the concentration of deep traps. It is assumed that trap formation is due to the formation of certain molecular structures below room temperature, most probably, with dissolved gas molecules.
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    Reaction kinetics and catalysis letters 66 (1999), S. 169-175 
    ISSN: 1588-2837
    Keywords: 1,3-pentadiene ; oxidation ; vanadyl ion ; HZMS-5
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different methods and vanadium compounds have been used to carry out proton exchange of zeolite HZSM-5 by vanadium cations. The catalysts are characterized by specific surface area, XRD, IR spectroscopy and TPD of ammonia. The catalysts’ activity in the oxidation of 1,3-pentadiene and the selectivity to carbonyl compounds are compared.
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    Reaction kinetics and catalysis letters 66 (1999), S. 63-70 
    ISSN: 1588-2837
    Keywords: Non-stationary kinetics ; alkylbenzene ; oxidation ; oxide catalysts
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A non-stationary kinetic model for deep oxidation of aromatic hydrocarbons based on the fragmentation theory approach is proposed. The model is simple and provides qualitative adequacy and good quantitative description of experimental results.
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    Reaction kinetics and catalysis letters 68 (1999), S. 237-242 
    ISSN: 1588-2837
    Keywords: Diols ; oxidation ; ozone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the oxidation of diols by ozone was investigated by a spectrophotometric method in the temperature interval of 277–304 K. The activation parameters of the reaction were determined.
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    Reaction kinetics and catalysis letters 68 (1999), S. 257-263 
    ISSN: 1588-2837
    Keywords: Alphatic alcohols ; oxidation ; ozone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of oxidation of aliphatic alcohols by ozone in aqueous solutions was investigated in the temperature interval of 292–317 K. The activation parameters of the reaction were determined. The dissociation energies of CH-bonds of the studied substrates were calculated with the use of the AM1 semiempirical method.
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  • 74
    ISSN: 1588-2837
    Keywords: Heteropoly acids ; dialkylquinones ; preparation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new method is proposed for synthesis of 2,6-dialkyl-1,4-benzoquinones by oxidation of 2,6-dimethyl and 2,6-di-tert-butylphenols with oxygen in a two-phase “water-organic” system in the presence of P−Mo−V heteropoly acids.
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  • 75
    ISSN: 1588-2837
    Keywords: Mechanism ; oxidation ; methyl phenyl sulfide ; hydrogen peroxide ; titanium-substituted heteropolytungstates ; peroxo complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Acid tetrabutylammonium salts of Ti(IV)-monosubstituted heteropolytungstate, PW11TiO40 5−, show high catalytic acitivity in the oxidation of methyl phenyl sulfide with hydrogen peroxide, while the corresponding tetrabutylammonium salts containing no protons are poor catalysts for this reaction.
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  • 76
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    Reaction kinetics and catalysis letters 66 (1999), S. 245-249 
    ISSN: 1588-2837
    Keywords: Montmorillonite clay ; peroxodiphosphate ; oxidation ; benzylic alcohols
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Clay-supported potassium peroxodiphosphate efficiently oxidizes benzylic alcohols to the corresponding aldehydes without overoxidation to acids. H3P2Og − as the active species.
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  • 77
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    Reaction kinetics and catalysis letters 67 (1999), S. 83-88 
    ISSN: 1588-2837
    Keywords: Manganese/ruthenium catalysts ; oxidation ; alkanes ; tert-butyl hydroperoxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Di- and trinuclear clusters of manganese and ruthenium were used as catalysts in the oxidation of alkanes in the presence oftert-butyl hydroperoxide as oxidant. The investigations reveal marked differences in the reactivity of the manganese and ruthenium catalysts though structurally they have similar coordination environment. The probable mechanism of hydroxylation in these systems is discussed.
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    Reaction kinetics and catalysis letters 67 (1999), S. 359-364 
    ISSN: 1588-2837
    Keywords: Mechanism ; oxidation ; alkylperoxo complexes of titanium(IV) ; 13C NMR spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Using13C and1H NMR spectroscopy, titanium(IV) alkylperoxo complexes Ti(OOtBu)n(OiPr)4−n with n=1, 2, 3 and 4 were characterized in the reaction of Ti(OiPr)4 withtBuOOH in CH2Cl2 and CDCl3.
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  • 79
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    Journal of inclusion phenomena and macrocyclic chemistry 16 (1993), S. 139-153 
    ISSN: 1573-1111
    Keywords: Synthesis ; Al-Omega ; Ga-Omega ; crystallisation kinetics ; X-ray diffraction ; IR ; MAS NMR ; sorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The synthesis and characterisation of zeolite Al- and Ga-Omega has been studied in the temperature range 383–413 K using tetramethyl ammonium hydroxide as a template. The evidence for framework gallium substitution was obtained from chemical analysis, X-ray diffraction, IR, solid state MAS NMR, thermoanalytical studies and ion exchange. Crystal morphology varied with the degree of isomorphous substitution of both Al and Ga and the synthesis temperature.
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  • 80
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    Journal of inclusion phenomena and macrocyclic chemistry 16 (1993), S. 189-197 
    ISSN: 1573-1111
    Keywords: calix[4]arene ; oxidation ; hemiketal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The formation of a stable calix[4]arene monohemiketal is described. X-ray crystallographic data provide conclusive evidence for the presence of a stabilizing hydrogen bond.
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    International journal of peptide research and therapeutics 6 (1999), S. 359-369 
    ISSN: 1573-3904
    Keywords: chemotaxis ; inflammation ; oxidation ; post-translational ; S100
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The functional importance of members of the S100 Ca2+-binding protein family is recently emerging. A variety of activities, several of whcih are apparently opposing, are attributed to S100A8, a protein implicated in embryogenesis, growth, differentiation, and immune and inflammatory processes. Murine (m) S100A8 was initially described as a chemoattractant (CP-10) for myeloid cells. It is coordinately expressed with mS100A9 (MRP14) in neutrophils and the non-covalent heterodimer is presumed to be the functional intracellular species. The extracellular chemotactic activity of mS100A8, however, is not dependent on mS100A9 and occurs at concentrations (10−13-10−11 M) at which the non-covalent heterodimer would probably dissociate. This review focuses on the structure and post-translational modifications of mS100A8/A9 and their effects on function, particularly chemotaxis.
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    International journal of peptide research and therapeutics 6 (1999), S. 359-369 
    ISSN: 1573-3904
    Keywords: chemotaxis ; inflammation ; oxidation ; post-translational ; S100
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The functional importance of members of the S100 Ca2+-binding protein family is recently emerging. A variety of activities, several of which are apparently opposing, are attributed to S100A8, a protein implicated in embryogenesis, growth, differentiation, and immune and inflammatory processes. Murine (m) S100A8 was initially described as a chemoattractant (CP-10) for myeloid cells. It is coordinately expressed with mS100A9 (MRP14) in neutrophils and the non-covalent heterodimer is presumed to be the functional intracellular species. The extracellular chemotactic activity of mS100A8, however, is not dependent on mS100A9 and occurs at concentrations (10-13–10-11 M) at which the non-covalent heterodimer would probably dissociate. This review focuses on the structure and post-translational modifications of mS100A8/A9 and their effects on function, particularly chemotaxis.
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    Interface science 1 (1993), S. 139-146 
    ISSN: 1573-2746
    Keywords: Silicon ; defects ; hyperfine interactions ; oxidation ; computer simulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract We assess several models for the environment of the P b center (Si dangling bond center) at the interface of Si(111) with its oxide. The comparison of hyperfine constants observed with those predicted using large cluster models favors a local structure in which there is an Si-Si bond within the oxide close to the Si dangling bond. Such Si-Si bonds are also suggested by a number of other experiments and are consistent with the “reactive layer” model proposed to rationalize a range of oxidation studies.
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