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  • Articles  (14)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Cellular and molecular life sciences 47 (1991), S. 1104-1118 
    ISSN: 1420-9071
    Keywords: Transaminase ; decarboxylase ; serine hydroxymethyltransferase ; pyridoxal 5′-phosphate ; enzyme mechanism ; stereochemistry ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Pyridoxal 5′-phosphate is a coenzyme for a number of enzymes which catalyse reactions at Cα of amino acid substrates including transaminases, decarboxylases and serine hydroxymethyltransferase. Using the X-ray coordinates for a transaminase, aspartate aminotransferase, and the results of stereochemical and mechanistic studies for decarboxylases and serine hydroxymethyltransferase, an active-site structure for the decarboxylase group is constructed. The structure of the active-site is further refined through active-site pyridoxyllysine peptide sequence comparison and a 3-D catalytic mechanism for the L-α-amino acid decarboxylases is proposed. The chemistry of serine hydroxymethyltransferase is re-examined in the light of the proposed decarboxylase mechanism.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 40 (1991), S. 181-185 
    ISSN: 1432-1041
    Keywords: Etizolam ; α-hydroxyetizolam ; healthy subjects ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of etizolam, a new thienodiazepine derivative, has been examined after single and multiple (0.5 mg tablet) (0.5 mg b.d for 1 week) oral therapeutic doses in healthy volunteers. The single-dose kinetic profile of etizolam suggested that absorption after oral dosage was reasonably rapid, the maximum plasma concentration (Cmax) being attained within 0.5–2 h in all subjects. The mean elimination half-life (t1/2) averaged 3.4 h. Consistent with this, steady-state concentration were rapidly achieved and accumulation was extremely limited. Predicted average plasma concentrations (Cp) did not differ significantly from those actually measured at steady-state, suggesting that the kinetics of etizolam was linear, at least at therapeutic doses. The mean wash-out t1/2 was comparable to the elimination t1/2 of the single dose, which means that the drug probably has no effect on hepatic microsomal enzymes and other kinetic variables after repeated dosing. At steady state plasma concentrations of the main metabolite, α-hydroxyetizolam, were higher and disappeared more slowly (mean t1/2 8.2 h) than those of the parent compound. Taken with the fact that in animals the metabolite shows almost the same potency of pharmacological action as etizolam, this suggests that it may contribute significantly to the clinical effects of the parent compound. Based on the kinetic characteristics of the parent drug and its metabolite, etizolam can be regarded as a short-acting benzodiazepine, with elimination kinetics between those of short-intermediate derivatives and ultra-rapidly eliminated benzodiazepines.
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  • 3
    ISSN: 1573-4919
    Keywords: phosphate-dependent glutaminase ; acute metabolic acidosis ; kinetics ; kidney tubules ; enterocytes ; hepatocytes ; brain tissue
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Summary We describe the kinetic modifications to mitochondrial-membrane-bound phosphate-dependent glutaminase in various types of rat tissue brought about by acute metabolic acidosis. The activity response of phosphate-dependent glutaminase to glutamine was sigmoidal, showing positive co-operativity, the Hill coefficients always being higher than 2. The enzyme from acidotic rats showed increased activity at subsaturating concentrations of glutamine in kidney tubules, as might be expected, but not in brain, intestine or liver tissues. Nevertheless, when brain and intestine from control rats were incubated in plasma from acutely acidotic rats enzyme activity increased at 1 mM glutamine in the same way as in kidney cortex. The enzyme from liver tissue remained unaltered. S0.5 and nH values decreased significantly in kidney tubules, enterocytes and brain slices preincubated in plasma from acidotic rats. The sigmoidal curves of phosphate-dependent glutaminase shifted to the left without any significant changes in Vmax. The similar response of phosphate-dependent glutaminase to acute acidosis in the kidney, brain and intestine confirms the fact that enzymes from these tissues are kinetically identical and reaffirms the presence of an ammoniagenic factor in plasma, either produced or concentrated in the kidneys of rats with acute acidosis.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 36 (1991), S. 439-464 
    ISSN: 1573-4889
    Keywords: V-A1 alloy ; Cr and Ti additions ; oxidation ; kinetics ; V2O5 ; Al2O3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior in air of pure vanadium, V-30Al, V-30Al-10Cr, and V-30Al-10Ti (weight percent) was investigated over the temperature range of 700–1000° C. The oxidation of pure vanadium was characterized by linear kinetics due to the formation of liquid V2O5 which dripped from the sample. The oxidation behavior of the alloys was characterized by linear and parabolic kinetics which combined to give an overall time dependence of 0.6–0.8. An empirical relationship of the form: ΔW/A=Bt + Ct1/2 + D was found to fit the data well, with the linear contribution suspected to be from V2O5 formation for V-30Al and V-30Al-10Cr, and a semi-liquid mixture of V2O5 and Al2O3 for V-30Al-10Ti. The parabolic term is presumed related to the formation of a solid mixture of V2O5 and Al2O3 for V-30Al and V-30Al-10Cr, and TiO2 for V-30Al-10Ti The addition of aluminum was found to reduce the oxidation rate of vanadium, but not to the extent predicted by the theory of competing oxide phases proposed by Wang, Gleeson, and Douglass. This was attributed to the formation of a liquid-oxide phase in the initial stages of exposure from which the alloys could not recover. Ternary additions of chromium and titanium were found to decrease the oxidation rate further, with chromium being the most effective. The oxide scales of the alloys were found to be highly porous at 900° C and 1000° C, due to the high vapor pressure of V2O5 above 800° C.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 36 (1991), S. 143-156 
    ISSN: 1573-4889
    Keywords: plasma nitriding ; Fe-18Cr-9Ni ; CrN precipitates ; nitrogen diffusion ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract To clarify the mechanism of plasma nitriding, we examined the optical microstructure, the hardness, the precipitation, and the concentration of dissolved nitrogen in Fe-18Cr-9Ni nitrided using plasma in the range of 723–823 K. Compared with ammonia-gas nitriding, the features of plasma nitriding are the formation of small chromium-nitride precipitates (CrN), the absence of an externally nitrided layer, the high concentration of dissolved nitrogen, and the high hardness (HV=1200). The diffusion coefficient of nitrogen in the present alloy was determined using the growth rate of the internally nitrided layer, based on calculations used in internal oxidation. Plasma- and gas-nitriding were also compared with respect to the growth rate of the nitrided layer.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 35 (1991), S. 107-137 
    ISSN: 1573-4889
    Keywords: iron ; oxidation in CO2+CO mixtures ; kinetics ; reaction mechanisms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxidation of high purity iron in CO 2 and CO2 + COmixtures at different total pressures (0.1–1 atm.) has been studied at 1000–1200°C. While paper I of this study emphasized studies of the relation between scale morphology and reaction kinetics, this paper focuses on the reaction mechanism during the initial oxidation involving growth of wüstite films and scales. The reaction behavior is analyzed in terms of coupled kinetics comprising a surface reaction and diffusional transport through the scale. A classical model derived by C. Wagner, based on the assumption that the properties and defect concentrations in the scale surface are exactly the same as in bulk wüstite equilibrated in CO 2 +CO mixtures, does not provide a satisfactory description of the reaction kinetics and the gas-pressure dependence of the surface reaction. As an alternative model, it is suggested that the gasous molecules/species interacts with the surface to form surface complexes, and that surface complexes withCO2 serve as preferred reaction sites for the surface reaction.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 35 (1991), S. 397-404 
    ISSN: 1573-4889
    Keywords: copper alloys ; nitridation ; kinetics ; scale structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract One of the characteristic features of Mn-Cu binary alloys nitrided by gaseous nitrogen is that one of the two constitutive elements (Mn) can form nitrides, while the other one (Cu) does not give any stable compound with nitrogen. The only mixed manganese-copper nitride is the CuMn 3 N compound. The reaction kinetics with nitrogen are very slow and there is no internal nitriding. For alloys containing less than 20 at.% Mn, nitrogen reacts very little. The nitride scale formed on the alloys of greater Mn concentrations is a mixed nitride whose formula is Cu 1−x Mn 3+x N. The techniques of examination used are SEM, EMA, and GDS analysis.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Mathematical geology 23 (1991), S. 325-347 
    ISSN: 1573-8868
    Keywords: hydrocarbons ; kinetics ; inverse methods
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Mathematics
    Notes: Abstract From a determination of the transformation matrix for three pyrolysis product experimental data sets, an examination is given of both the applicability of the laboratory experimental data to the modeling of oil cracking in a sedimentary basin, and of the appropriateness of an inverse model. The results of the laboratory experimental data sets, which were done under different thermodynamic conditions and using different sources, show that the transformation matrix varies over each data set and also with time. Therefore, it is necessary to check the data sets before applying them to a basin for hydrocarbon modeling. The laboratory experimental data taken at lower temperature and over longer times appear more pertinent for the construction of an oil-cracking kinetic model suitable for geologic conditions.
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  • 9
    ISSN: 1435-1536
    Keywords: Polystyrene seed ; poly(butyl acrylate-methacrylic acid) shell ; particle mophology ; location of carboxylic groups ; kinetics
    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 Polystyrene (PS) (1)/Poly(n-butyl acrylate (BA)-methacrylic acid (MAA)) (2) structured particle latexes were prepared by emulsion polymerization using monodisperse polystyrene latex seed (118 nm) and different BA/MAA ratios. Three main aspects have been investigated: i) the polymerization kinetics; ii) the particle morphology as a function of reaction time; iii) the distribution of MAA units between the water phase and the polymer particles. The amount of MAA in the shell copolymer was found to be the main factor controlling the particle shape and morphology. The shape of the structured particles was, generally, non-spherical, and the shape irregularities increased as a particles was, generally, non-spherical, and the shape irregularities increased as a function of reaction time. At the beginning of the second stage reaction, new small particles were observed, which coalesced onto the PS seed as the polymerization proceeded. The distribution of the MAA groups in the latex particles and the serum was analyzed by alkali/back-acid titration, using ionic exchanged latexes. No MAA groups were detected in the latex serum. Due to the lowTg of the BA-MAA copolymers, alkali conductimetric titrations accounted for all the MAA groups on and within the polymer particles. Therefore, for these systems, this method is not only limited to a thin surface layer, as it is often assumed.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 12 (1991), S. 137-151 
    ISSN: 1573-0662
    Keywords: Soot particles ; polycyclic aromatic hydrocarbons ; NO2 ; HNO3 ; heterogeneous reactions ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract An experimental technique for studying atmospheric heterogeneous reactions of polyaromatic hydrocarbons (PAH) on particle surfaces is reported. Particle bound organics were reacted in a 200 liter Teflon continuous stirred tank reactor (CSTR), with vapor phase oxidants. To provide a source of chemically stable particles for the CSTR, soot particles from a residential wood stove were first introduced during under darkness into a 25 m3 outdoor Teflon chamber. Air containing the particles was then added at a constant flow to the CSTR. The rates of heterogeneous reactions were obtained by comparing reacted particle samples with unreacted ones. The derivation of rate expressions for heterogeneous reactions in the CSTR is described. The use of the technique for a study of the nitration of selected soot particle bound PAH species by NO2 and HNO3 is demonstrated.
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