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  • kinetics  (107)
  • Springer  (107)
  • American Chemical Society
  • American Meteorological Society
  • 1995-1999  (70)
  • 1990-1994  (37)
  • 1965-1969
  • 1999  (70)
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  • Springer  (107)
  • American Chemical Society
  • American Meteorological Society
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  • 1995-1999  (70)
  • 1990-1994  (37)
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  • 1
    ISSN: 1572-8927
    Keywords: Solvolysis ; kinetics ; aqueous solvent mixtures ; Co(III) complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the solvolysis of [Co(CN)5Cl]3− have been investigated in water +2-methoxyethanol and water + diethylene glycol mixtures. Although the addition of these linear hydrophilic cosolvent molecules to water produces curvature in the variation of log(rate constant) with the reciprocal of the dielectric constant, their effect on the enthalpy and entropy of activation is minimal, unlike the effect of hydrophobic cosolvents. The application of a Gibbs energy cycle to the solvolysis in water and in the mixtures using either solvent-sorting or TATB values for the Gibbs energy of transfer of the chloride ion between water and the mixture shows that the relative stability of the emergent solvated Co(III) ion in the transition state compared to that of Co(CN)5Cl3− in the initial state increases with increasing content of cosolvent in the mixture. By comparing the effects of other cosolvents on the solvolysis, this differential increase in the relative stabilities of the two species increases with the degree of hydrophobicity of the cosolvent.
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  • 2
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    Journal of applied electrochemistry 29 (1999), S. 191-200 
    ISSN: 1572-8838
    Keywords: cyclic redox reaction ; dissolution ; kinetics ; manganese dioxide ; mechanism ; pyrite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract This paper describes a study of the kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite through leaching and electrochemical parameters. Manganese(iv) was found to dissolve mainly through reduction by the ferrous ion generated during oxidation of pyrite by the ferric ion. The oxidation which is slower and rate controlling may proceed through two different reactions, one producing S0 and the other SO42−. Manganese dissolution runs at the same rate as that of pyrite oxidation by maintaining ferrous ion concentration at a much lower level than that of ferric. Kinetic equations based on corrosion coupling principles are developed to explain the observed leaching behaviour.
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  • 3
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    Journal of solution chemistry 23 (1994), S. 483-500 
    ISSN: 1572-8927
    Keywords: Thermodynamics ; kinetics ; chemical relaxation ; temperature-jump ; amplitudes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Amplitudes of chemical relaxation signals can provide useful information as to the thermodynamics of coupled chemical reactions. The temperature-jump technique has been used to investigate the thermodynamic behavior of the Nickel(II)-3,5-dinitrosalicylate system in buffer solution, where complex formation steps are coupled to proton transfer steps. The analysis of the relaxation curves is based on the transformation of a set of coupled elementary reactions into a set of uncoupled ‘normal reactions.’ By analogy with classical titrations, the experiments have been performed by changing the metal ion concentration at constant ligand concentration and pH. Each measured amplitude is associated in this way to a point of a ‘dynamic titration’ and a procedure is formulated by which the values of the equilibrium constants and enthalpies of the normal reactions are simultaneously obtained by simple linear plots. From the dependence of these parameters on suitable functions of the concentrations of the reactants the values of ΔG° and ΔH° of the individual steps are derived. It is shown that the addition of a buffer (instead of an indicator) influences the stoichiometric coefficients of the normal reaction in such a way that measurable amplitudes are produced in systems that, as the presently investigated, in unbuffered solution would remain insensitive to the external perturbation. The circumstances under which the dynamic method offers advantages over the classical techniques are discussed.
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  • 4
    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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  • 5
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    Cellulose 1 (1994), S. 26-56 
    ISSN: 1572-882X
    Keywords: low-temperature degradation ; kinetics ; mechanisms ; electrical insulation ; transformers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A critical review is given of the degradation of cellulose in the low-temperature region (below about 300°C) of power transformer operation. The large number of kinetic studies, under a variety of environmental conditions from Kraft paper in insulating oil, to cotton and paper in oxygen, are considered in terms of a first-order polymer chain scission model. In many cases, the data are replotted to suit the model. A common activation energy of 111±6 kjmol−1 is calculated and it is shown that the pre-exponential factor, rather than the activation energy, is sensitive to the oxidizing nature of the environment and the susceptibility to degradation of the material. The chemical mechanisms of degradation are reviewed, and conclusions and recommendations are made regarding chemical condition monitoring and life prediction of electrical insulation.
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  • 6
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    Catalysis letters 27 (1994), S. 79-90 
    ISSN: 1572-879X
    Keywords: kinetics ; carbon ; oxygen ; recombination ; rhodium ; surface characterisation ; XPS ; AES
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different mechanisms of atomic carbon and oxygen recombination on a rhodium surface are studied with Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The kinetics of adsorbed carbidic carbon oxidation (carbon coverageθ c ≈ 0.1–0.3 ML) by gas-phase oxygen that proceeds by a Langmuir-Hinshelwood reaction mechanism, provides the value of the activation energy for recombination (E rec ⇂t ≈ 170±20 kJ/mol).E rec ⇂t depends slightly on the carbon coverage. An Eley-Rideal type of reaction was observed for adsorbed oxygen and atomic gas-phase carbon recombination which occurs in a dynamic regime. The low value found for the activation energy (near zero) is consistent with the mechanism that this exothermic reaction is too fast for energy dissipation into the substrate; the energy is mainly transferred into translational, vibrational and rotational energy of CO.
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  • 7
    ISSN: 1572-8900
    Keywords: Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    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 degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
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  • 8
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    Topics in catalysis 1 (1994), S. 305-314 
    ISSN: 1572-9028
    Keywords: non-Langmuir ; kinetics ; non-linear dynamics ; oscillations ; chaos ; self-organization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of a catalytic reaction is frequently formulated in terms of simple concepts of the Langmuir type. Apart from limitations arising from the non-uniformity of the catalyst's surface and from the coverage dependence of the rate “constants”, several other complications may come into play. These may arise on the “quantum level” where energy flow between the various degrees of freedom may cause failure of simple transition state theory, as well as on the “continuum level” where formulation of rate equations in terms of coupled non-linear differential equations may give rise to a rich scenario of spatio-temporal self-organization, including kinetic oscillations, chaos, and formation of concentration patterns. Several of these phenomena are illustrated by selected examples.
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  • 9
    ISSN: 1572-8757
    Keywords: micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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  • 10
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; platinum ; palladium ; sulfur dioxide ; alumina ; zirconia ; activity ; acidity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated γ-alumina or zirconia compared to γ-alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/γ-alumina, Pt/zirconia, Pd/γ-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/γ-alumina, and Pd/zirconia is less active than Pd/γ-alumina.
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  • 11
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    Catalysis letters 60 (1999), S. 51-57 
    ISSN: 1572-879X
    Keywords: furfural hydrogenation ; Cu/carbon catalysts ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Furfural hydrogenation over copper dispersed on three forms of carbon – activated carbon, diamond and graphitized fibers – were studied. Only hydrogenation of the C=O bond to form either furfuryl alcohol or 2‐methyl furan occurred at temperatures from 473 to 573 K. Reduction at 573 K gave the most active catalysts, all three catalysts had activation energies of 16 kcal/mol, and turnover frequencies were 0.018–0.032 s-1 based on the number of Cu0 + Cu+ sites, which were counted by N2O adsorption at 363 K and CO adsorption at 300 K, respectively. The Cu/activated carbon catalyst showed no deactivation during 10 h on stream, in contrast to the other two catalysts. A simple Langmuir–Hinshelwood model invoking two types of sites was able to fit all kinetic data quite satisfactorily, thus it was consistent with the presence of both Cu0 and Cu+ sites.
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  • 12
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    Catalysis letters 60 (1999), S. 167-171 
    ISSN: 1572-879X
    Keywords: ammonia decomposition ; iron catalyst ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k0 exp (Ea/RT)pNH3. The activation energy of the ammonia decomposition process has been found for samples with potassium as E a= 96 kJ/mol, for samples without potassium as E a= 87 kJ/mol.
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  • 13
    ISSN: 1572-8757
    Keywords: kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 14
    ISSN: 1572-879X
    Keywords: hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
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  • 15
    ISSN: 1436-5073
    Keywords: flow injection analysis (FIA) ; mercury ; porphyrin ; kinetics ; spectro-photometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS4) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min−1 for Hg(II) withm-Cl-TPPS4 in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 μl), the method's relative standard deviation was 0.82% (n = 12) at 5.0 μg ml−1 mercury, with a linear range of 0–12.0 μg ml−1 and an analytical frequency of 60h−1. The detection limit (3σ) was 0.025 μg ml−1. Interference studies showed that most metal ions co-existing with Hg2+ could be tolerated at 100-fold excess levels, but Zn2+, Cu2+ and Mn2+ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.
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  • 16
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    Nutrient cycling in agroecosystems 39 (1994), S. 39-42 
    ISSN: 1573-0867
    Keywords: Controlled release fertilizers ; kinetics ; mechanism ; nutrient supply ; rate of release ; slow release fertilizers (SRF)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Individual granules within a given granule population of a slow-release fertilizer (SRF) have a different release pattern. The populations studied differed both in relation to the time delay before the start of the release process and to the duration of the release. An association between a short delay period and a rapid release was found. The random reease distribution can be approximated using first-order rate equations. In cases, a term describing a “lag” period should be added. The distribution of release timing among the fertilizer granules may allow a long-lasting nutrient supply to the plant, as long as there are enough granules within the root zone to allow a uniform supply pattern.
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  • 17
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    Journal of statistical physics 95 (1999), S. 23-43 
    ISSN: 1572-9613
    Keywords: model alloy ; Monte Carlo ; elastic interactions ; phase separation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We study via Monte Carlo simulations the influence of elastic interactions on the ordering and decomposition of a two-dimensional model binary alloy with antiferromagnetic nearest and ferromagnetic next nearest neighbor type interactions following a quench into the coexistence region. The elastic interaction leads to the development of a platelet morphology for the segregated ordered and disordered regions. A length scale characterizing the coarsening process follows a law of the type R=a+bt 1/3 with the growth b decreasing with the amount of ordered phase; this appears to be due to the presence of anti-phase boundaries between neighboring domains ordered on different sublattices which are difficult to eliminate. The application of uniaxial external stress results in “rafting” of the domains. Many of the simulation results are in agreement with experimentally observed effects in nickel-base superalloys.
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  • 18
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    Journal of thermal analysis and calorimetry 55 (1999), S. 9-19 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN1. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol−1. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPNg. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g−1 and -3.85±0.03 kJ g−1, respectively from DSC and HFC measurements on IPN1 samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol−1 was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase.
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  • 19
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    Journal of thermal analysis and calorimetry 55 (1999), S. 233-241 
    ISSN: 1572-8943
    Keywords: cadmium(II) atom ; kinetics ; non-isothermal decomposition ; Schiff-base compound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystal C81H78N12O6Cd3 was synthesized and its structure was determined by single crystal X-ray diffraction method. The complex crystallizes in the monoclinic system space group P21/n with cell parameters, a=15.959(4) Å, b=26.222(3) Å, c=25.907(6) Å, β=101.60(2)°. The non-isothermal kinetics of the crystal was studied by use of non-isothermal TG and DTG curves. The kinetic parameters were analyzed by means of integral and differential methods, and mechanism functions of the thermal decomposition reaction for its second step were proposed. The kinetic equation of thermal decomposition is expressed as: dα/dt=Aexp(-E/RT)1.5(1-α)4/3[1/(1-α)1/3-1]−1. The average values of E(kJ mol−1) and lnA/s−1 are 339.25, 43.95, respectively.
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  • 20
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    Journal of thermal analysis and calorimetry 55 (1999), S. 301-309 
    ISSN: 1572-8943
    Keywords: dehydroxylation ; goethite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermal dehydroxylation of aluminuous goethites [1] synthesised from a ferrous salt has been re-examined using the general reaction order kinetic law. The utilised data processing was based on the procedures employed by dissolution kinetics. Recalculation of the activation energies EA of the dehydroxylation yielded the values 130, 132, 128, and 123 kJ mol−1 for pure goethite, goethite with 10, 20, and 30 mol% Al substitution, respectively. The values of EA are in a good agreement with those given for goethite in literature. The EA values are linearly related with the chemically bound excess H2O/OH− in the crystal lattice that is apparently influenced by Al substitution.
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  • 21
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    Journal of thermal analysis and calorimetry 55 (1999), S. 841-849 
    ISSN: 1572-8943
    Keywords: cobalt(II)-dothiepin ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The complexes of cobalt(II) with dothiepin (DOT) hydrochloride have been studied for kinetics of thermal degradation by thermogravimetric analysis (TG) and derivative thermogravimetric studies (DTG) in a static nitrogen atmosphere at a heating rate of 10° C min−1. A general mechanism of thermal decomposition is advanced involving dehydration and decomposition process for both organic and inorganic ligands. The thermal degradation reactions were found to proceed in three steps having an activation energy in the range 6.75–170 kJ mol−1. Thermal decomposition kinetics parameters were computed on the basis of thermal decomposition data.
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  • 22
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    Journal of thermal analysis and calorimetry 56 (1999), S. 297-303 
    ISSN: 1572-8943
    Keywords: β-zeolite ; coke ; cumene ; kinetics ; regeneration ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An accurate description of coke burn off is obtained from a catalyst based on β-zeolite and used for benzene alkylation with propylene giving cumene by using the thermogravimetric technique. A simple empirical kinetic model was successfully applied to interpolate the data of thermogravimetric analysis performed on samples after partial burn off. Different temperatures, partial pressures of oxygen and gas flow rates were the variables studied in order to calculate the apparent rates and the activation energy for the coke oxidation reaction and to outline the best conditions for the industrial regeneration procedure of our proprietary catalyst PBE-1 for cumene synthesis. Combining the unusually long lifetime per reaction cycle with the optimized regeneration procedure leads to an outstanding overall catalyst life.
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  • 23
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    Journal of thermal analysis and calorimetry 56 (1999), S. 953-958 
    ISSN: 1572-8943
    Keywords: differential scanning calorimeter ; kinetics ; oil shale ; pyrolysis ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this research, non-isothermal pyrolysis behavior and kinetics of three oil shales were studied by thermal analysis methods. All the thermal effects were endothermic and no exothermic region was observed in DSC curves. When oil shales are heated in nitrogen atmosphere in TG/DTG, two different mechanisms causing loss of mass were observed. The region between ambient temperature and 500 K was distillation. The second mechanism was visbreaking and cracking and it was observed between the region 500 and 800 K. Kinetic parameters of all the samples are determined by Coats and Redfern method and the results are discussed with regard to their accuracy and the ease of interpretation.
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  • 24
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1461-1473 
    ISSN: 1572-8943
    Keywords: CaCO3 ; densification ; kinetics ; Li2CO3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pressureless sintering of CaCO3 was carried out, with Li2CO3 (from 0.5 to 8 wt%) as an additive, under different pressures of CO2. Densification occurs between 600 and 700°C. Sintering above the eutectic temperature (T〉662°C) leads to the decomposition of calcium carbonate and the materials become expanded. At 620° under 1 kPa of CO2, a relative density of 96% is reached. Li2CO3 enhances the densification process and grain growth of calcium carbonate. CO2 pressure slows down densification and grain growth kinetics. These results are explained by the influence of carbonate and calcium ion vacancies on the sintering mechanisms.
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  • 25
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    Journal of thermal analysis and calorimetry 58 (1999), S. 383-391 
    ISSN: 1572-8943
    Keywords: 1-aminopyrene (apyr) ; N-(2-pyridylmethylene)-1-pyrenylamine (pmpa) ; kinetics ; palladium(II)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition studies for two palladium(II) complexes Pd(apyr)2Cl2 and Pd(pmpa)Cl2 (apyr=1−aminopyrene and pmpa=N−(2−pyridylmethylene)−1−pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, Šesták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.
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  • 26
    ISSN: 1572-8943
    Keywords: first order autocatalytic reaction ; HNNC ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the first order autocatalytic decomposition reaction of highly nitrated nitrocellulose (HNNC, 14.14%N) was studied by using thermogravimetry (TG). The results show that the TG curve for the initial 50% of mass-loss of HNNC can be described by the first order autocatalytic equation $$\frac{{{\text{d}}y}} {{dt}} = - 10^{16.4} \exp \left( { - \frac{{210380}} {{RT}}} \right)y - 10^{16.7} \exp \left( { - \frac{{171205}} {{RT}}} \right)y(1 - y)$$ and that for the latter 50% mass-loss of HNNC described by the reaction equations $$\frac{{dy}} {{dy}} = - 10^{16.3} \exp \left( { - \frac{{169483}} {{RT}}} \right)y\quad (n = 1)$$ and $$\frac{{dy}} {{dt}} = - 10^{16.8} \exp \left( { - \frac{{165597}} {{RT}}} \right)y^{2.61} \quad (n \ne 1)$$
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    Journal of thermal analysis and calorimetry 55 (1999), S. 173-185 
    ISSN: 1572-8943
    Keywords: IRS ; kinetics ; mechanism ; nitro aromatic ; TA
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics and mechanism of the initial stage of thermal decomposition of 2,4,6-trinitro toluene (TNT), a widely used high explosive, have been studied, together with its morphology and evolved gaseous products using thermogravimetry (TG), differential thermal analysis (DTA), infrared spectroscopy (IR) and hot-stage microscopy. The kinetics of the thermolysis has been followed by IR after suppressing volatilisation by matrixing and by isothermal TG without suppressing volatilisation to simulate actual user conditions. The best linearity was obtained for Avrami-Erofeev equation for n=1 in isothermal IR and also in isothermal TG. The activation energy was found to be 135 kJ mol−1, with logA (in s−1) 12.5 by IR. The effect of additives on the initial thermolysis of TNT has also been studied. Evolved gas analysis by IR showed that CO2, NO2, NO and H2O are more dominant than N2O, HCN and CO. The decomposition involves the initial rupture of the C-NO2 bond, weakened by hydrogen bonding with the labile hydrogen atom of the adjacent CH3 group, followed by the abstraction of the hydrogen atom of the methyl group by NO2, generated in the initial step.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 691-698 
    ISSN: 1572-8943
    Keywords: activation energy ; kinetics ; solid-state reactions ; superconductors ; thermogravimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetric in situ measurements of oxygen loss from (RE)Ba2Cu3O6 samples (RE=Y, Nd, Er) heated isothermally in a relatively high dynamic vacuum were made with a Cahn RG electrobalance. Single-phase orthorhombic samples of composition (RE)Ba2Cu3O7-x (highest oxygen content) were synthesized from stoichiometric (1:2:3) mixtures of high-purity (RE)2O3, BaCO3 and CuO. The original 1:2:3 mixture was prepared by the two-stage procedure described earlier. The crystal structure of the sample in the original orthorhombic phase was controlled by the X-ray powder method (CuKα radiation) using a Stadi P Stoe diffractometer with a position-sensitive detector. The decomposition curves are described by the sum of exponential terms corresponding to rapid and slow first-order processes in which differently sized grains of the powder samples are involved. The activation energies are estimated from appropriate Arrhenius plots.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 779-788 
    ISSN: 1572-8943
    Keywords: cobalt ; dynamic and isothermal methods ; kinetics ; molybdotellurates ; nickel
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Molybdotellurates [M(H2O)6]3·[TeMo6O24], with M=Ni(II) and Co(II), were synthesized and characterized by single-crystal X-ray diffraction for compound 1 and X-ray powder diffraction for compound 2, EDAX, IR, electronic spectra in the solid phase and in solution, and magnetic properties. Thermogravimetry and differential scanning calorimetry of both compounds revealed a loss of 11 water molecules through an endothermal process with ΔH=800 kJ mol−1 for the nickel compound and ΔH=833 kJ mol−1 for the cobalt compound. The residual compounds were characterized by chemical analysis, IR and XPS spectroscopy
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    Journal of thermal analysis and calorimetry 55 (1999), S. 817-831 
    ISSN: 1572-8943
    Keywords: kinetics ; Schiff-bases
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Cobalt(II), nickel(II), copper(II) and zinc(II) complexes of two new Schiff-bases, citronellal anthranilic acid and citronellal-5-bromoanthranilic acid have been synthesized. On the basis of spectral, magnetic and thermal data, octahedral structure was assigned to all complexes [ML2(H2O)2]. Thermal decomposition of these complexes was studied by TG. Kinetic parameters, viz activation energy, E, pre-exponential factor, A, and order of reaction, n, were calculated from the TG curves using mechanistic and non-mechanistic integral equations.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 17-26 
    ISSN: 1572-8943
    Keywords: kinetics ; reaction controlled thermal analysis ; stepwise isothermal analysis ; thermogravimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The Reaction Controlled Thermal Analysis techniques, RCTA, are very useful both in thermogravimetric and dilatometric studies. In the present paper this big family of techniques is divided into three main classes: Quasi-Isothermal techniques (QIA); Controlled Reaction Rate Thermal Analysis (CRTA) and Reaction (Event) Controlled Heating Rate Adaption. After a short presentation of these techniques and the general advantages of RCTA, two examples of kinetic studies on thermal decomposition of Ba- and Ce oxalates by using Stepwise Isothermal Analysis, SIA, introduced by the author is presented and discussed.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 783-792 
    ISSN: 1572-8943
    Keywords: complex process ; DSC ; isoconversional methods ; kinetics ; model-free kinetics ; peak maximum evolution methods ; simulations
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In the case of a complex mechanism of two parallel independent reactions, peak maximum evolution methods and model-fitting methods give only a mean value of the kinetic parameters, while isoconversional methods are useful to describe the complexity of the mechanism. Isothermal and non-isothermal isoconversional methods can be used to elucidate the kinetics of the process. Nevertheless, isothermal isoconversional methods can be limited by restrictions on the temperature regions experimentally available because of duration times or detection limits.
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  • 33
    ISSN: 1572-8943
    Keywords: cobalt ; dmit ligand ; kinetics ; non-linear method ; Zsakó method
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In this work, a cobalt complex with dmit (1,3-dithiol-2-thione-4,5-dithiolate) as ligand was prepared and its thermal stability was studied by thermogravimetric analysis and kinetics by means of the Zsakó method and a non-linear method. For both methods, numerical binomial and polynomial filters were used, where points in the central interval were utilized.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1107-1113 
    ISSN: 1572-8943
    Keywords: differential scanning calorimetry ; induction period ; kinetics ; vulcanisation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Vulcanisation of rubber compounds was studied by DSC under isothermal and non-isothermal conditions. The parameters of an Arrhenius-like equation describing the temperature dependence of induction period have been obtained both from isothermal and non-isothermal measurements. A new method for obtaining the kinetic parameters from non-isothermal measurements, based on the dependence of onset temperature of vulcanisation peak on heating rate, is presented. Also, a procedure for the evaluation of temperature difference between the furnace and sample is proposed. It has been shown that the treatment of non-isothermal DSC measurements gives the kinetic parameters free of systematic errors. The new method can also be used for studying other reactions exhibiting the induction period.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 699-705 
    ISSN: 1572-8943
    Keywords: interaction in solid phase ; lithium carbonate ; lithium orthosilicate ; kinetics ; solid electrolytes
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m2g-1 instead of aerosil with one of 175 m2g-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 755-761 
    ISSN: 1572-8943
    Keywords: crystallization ; DTA ; kinetics ; Kissinger plot ; lithium diborate glass
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystallization process of Li2B4O7 in the glass of stoichiometric composition, characterized by the crystal growth of pre-existing nuclei, was analyzed kinetically by means of DTA. Because the number of pre-existing nuclei for the subsequent growth varies depending on the cooling rate of the glass-forming melt and heating rate of the as-prepared glass, a modified Kissinger plot was applied for evaluating the apparent activation energy to the crystal growth in the glass samples with three different thermal histories, i.e., the pre-annealed, slowly quenched and quickly quenched glasses. The process was characterized by the three dimensional growth of pre-existing nuclei with the apparent activation energy of ca 340 kJ mol−1.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 603-610 
    ISSN: 1572-8943
    Keywords: coprecipitation ; ferrite ; kinetics ; sintering
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The authors report on a non-isothermal kinetic investigation (at constant heating rate) of the sintering of manganese and nickel-zinc ferrite powders prepared by coprecipitation. The kinetic results point to the thermal compaction of the powders, which occurs mainly in the intermediate stage of sintering. A comparative study was performed in order to determine the influence of the sample characteristics (such as chemical nature, density and shape) and the heating rate on the kinetics and mechanism of the compaction.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 843-849 
    ISSN: 1572-8943
    Keywords: adiabatic calorimetry ; kinetics ; non-parametric kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The non-parametric kinetics (NPK) method has been recently developed for the kinetic treatment of thermoanalytical data. The most significant feature of this method is its ability to provide information about the reaction kinetics without any assumptions either about the functionality of the reaction rate with the degree of conversion or the temperature. This paper presents the results of the application of the method to adiabatic calorimetry. Some data have been obtained by numerical simulation, but also the thermal decomposition of DTBP, a well known first order reaction, has been studied, being the obtained results in good agreement with literature.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 829-833 
    ISSN: 1572-8943
    Keywords: dolomite ; kinetics ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition reactions of calcitic dolomite were investigated. Simultaneous TG/DTG/DTA were applied under non-isothermal conditions. From the recorded curves, the activation energies, pre-exponential factors and thermodynamic parameters of activation were calculated for the two thermal decomposition steps.
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    Journal of thermal analysis and calorimetry 58 (1999), S. 215-223 
    ISSN: 1572-8943
    Keywords: adiabatic calorimetry ; kinetics ; Kissinger method
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Traditionally, the kinetic treatment of adiabatic calorimetry data has been based on the results of one or more experiments, but always with the assumption of the kinetic model that the reaction follows to calculate the kinetic parameters. In this paper a method for the determination of the activation energy that uses a set of adiabatic calorimetry data is developed. To check the method, the thermal decompositions of two peroxides were studied.
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  • 41
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    Keywords: coordinationcompounds ; CRTA ; kinetics ; polymerization ; pyrolysis ; quasi-equilibrium ; TG ; thermolysis ; volatility
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Quasi-equilibrium thermogravimetry (variant of CRTA) is put to use as an express method of thermoanalytical screening for volatile compounds. During the experiments for P—T relationship calculations (running with several calibrated standard sample holders) the non-volatile (polymerized) residue is formed (and is decomposed with further temperature rising). Thermogravimetric data are used for the calculation of the kinetic parameters for the polymerization reaction, taking place (concurrently with the evaporation) in the melt of the studied volatile compound.
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    Journal of thermal analysis and calorimetry 58 (1999), S. 447-453 
    ISSN: 1572-8943
    Keywords: coal ; combustion reaction ; kinetics ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The combustion behavior of Shuangya Mountain (SYM) coal dust has been investigated by means of TG in this paper. The reaction fraction α can be obtained from isothermal TG data. The regressions of g(α), an integral function of α vs. t for different reaction mechanisms were performed. The mechanism of nucleation and nuclei growth is determined as the controlling step of the coal dust combustion reaction by the correlation coefficient of the regression, and the kinetic equation of the SYM coal dust combustion reaction has been established.
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    Structural chemistry 10 (1999), S. 433-437 
    ISSN: 1572-9001
    Keywords: Positronium Chemistry ; kinetics ; spin exchange reactions ; paramagnetic 3d complexes
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The rate constants, k CR, of ortho- into para-positronium conversion reactions promoted by paramagnetic 3d complexes are linearly correlated with the electron delocalization, β, of unpaired metal electrons caused by ligands, β being the ratio between the inter-electronic repulsion parameters in complexes and in the free gaseous ions. By applying a procedure previously described the β values of MnII, CoII, NiII complexes with dimethylurea were deduced from the mentioned correlations and compared with those of complexes with urea obtained both by the method of Ps reactions here applied and that based on UV-Vis absorption spectroscopy.
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  • 44
    ISSN: 1572-8986
    Keywords: Arc ; gliding arc ; gas temperature ; electron temperature ; ion composition ; ion bombardment ; liquid electrode ; dye oxidation ; kinetics
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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 plasma–solution interaction processes for gliding and “point” arcs between the aqueous solution surface and the metal electrode in the gas phase are studied. The plasma, liquid, and surface zones are taken into consideration. The electric field strength is measured, and the gas and electron temperatures and ion composition are estimated for the plasma zone. The cathode fall, water vaporization rate, and active species current yield due to the radiation chemistry mechanism are determined for the surface zone. The efficiency of oxidation of iodine ions and organic dyes by different types of discharge in the liquid zone are investigated. The difference in action of the various discharge types may be connected with various influences of the plasma and surface zone on the oxidation processes.
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    Molecular and cellular biochemistry 131 (1994), S. 43-47 
    ISSN: 1573-4919
    Keywords: angiotensinogen ; kinetics ; recombinant protein ; renin ; species specificity ; transgenic mouse
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The renin-angiotensin system (RAS) is the most important regulator of electrolyte homeostasis and blood pressure. Our recently generated transgenic mice carrying either the human renin (hREN) or human angiotensinogen (hANG) genes did not develop hypertension but dual gene strains obtained by cross-mating separate lines of mice exhibited a chronically sustained increase in blood pressure, suggesting the presence of species-specific reactivity between renin and angiotensinogen. In order to examine this specificity, the present study was designed to perform a strictly comparative study on hydrolysis of hANG by hREN and mouse submandibular renin (mREN)in vitro by using pure proteins. The recombinant hANG (rhANG) and the synthetic human-type tridecapeptide (hTDP), Asp-Arg-Val-Tyr-Ile-His-Pro-Phe-His-Leu-Val-Ile-His, corresponding to the N-terminal sequences of hANG, were used to determine the species specificity of recombinant hREN (rhREN) and mREN. While hTDP was cleaved by both rhREN with similar Km and with the same order of kcat, rhANG was cleaved by mREN with 16.7-fold higher Km and with 28.2-fold lower kcat than by rhREN. These results showed that kcat/Km value of mREN for rhANG was 468-fold lower than that for rhREN acting on rhANG.
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    Molecular and cellular biochemistry 197 (1999), S. 195-201 
    ISSN: 1573-4919
    Keywords: phospholipase D ; phosphatidylinositol 4,5-bisphosphate ; neomycin ; kinetics
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The kinetics of phosphatidylcholine-specific phospholipase D activated by phosphatidylinositol 4,5-bisphosphate (PIP2) and inhibition by neomycin were studied in an enzyme preparation partially purified from human hepatocarcinoma cell line. It was found that phospholipase D was marginally activated by phosphatidyl-4-phosphate (PIP) and phosphatidylethanolamine (PE). In contrast, it was considerably activated by PIP2 in different concentration of phosphatidylcholine (PC). Sphingomyelin (SM), lysophosphatidylcholine (LPC) and phosphatidylserine (PS) were neither substrates nor inhibitors of the phospholipase D. PIP2 induced an allosteric effect on phospholipase D and a negative cooperative effect with respect to phosphatidylcholine as indicated in the Lineweaver-Burk plot. In the absence of PIP2, a straight line was obtained, whereas a downward concave curve was observed in the presence of 25 μM of PIP2. The Hill coefficient and the apparent Km of phosphatidylcholine in the presence of 25 μM PIP2 were calculated to be 0.631 and 10.79 mM, respectively. PIP2 also increased the maximal velocity (Vmax) of the phospholipase D reaction, suggesting that the affinity of substrate to enzyme was decreased, and the turnover number of the enzyme (kcat) was increased by PIP2. The activation of phospholipase D by PIP2 was dose dependent up to 50 μM of PIP2. The Ka of PIP2 was 15.8 mM. Neomycin, a polycationic glycoside, was shown to be an uncompetitive inhibitor of phospholipase D, and revealed the formation of a neomycin-PIP2 complex. The Ki of neomycin was estimated to be 8.7 mM.
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  • 47
    ISSN: 1573-4889
    Keywords: niobium ; oxidation ; morphology ; kinetics ; stresses
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of niobium at high temperature (900°C) leads to reaction products with “exotic” morphologies. Morphological and kinetics analysis have been undertaken with Nb platelets. A growth mechanism of the oxide at the edges of the platelet is proposed.
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    Oxidation of metals 42 (1994), S. 223-237 
    ISSN: 1573-4889
    Keywords: kinetics ; scale ; oxidation ; zirconium ; purity
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    Notes: Abstract The oxidation kinetics of zirconium of different purities were studied over the temperature range of 600–1300°C (α- and β-phases). The structure of the oxidized specimens was examined. TGA, XRD, EPMA, SEM, metallographic analysis, and microhardness measurements were carried out. Impurity elements were found to increase the oxidation rate of technical zirconium. The mechanism of the effect of impurity elements on zirconium oxidation was shown to differ for the α- and β-phases. Activation energies were calculated for the parabolic and linear stages of oxidation.
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    Oxidation of metals 42 (1994), S. 249-263 
    ISSN: 1573-4889
    Keywords: kinetics ; scale ; oxidation ; hafnium ; purity
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of hafnium of different purities were studied in the temperature range of 800–1200°C. This paper concerns the structure studies of the oxidized samples. TGA, XRD, SEM methods, and microhardness measurements were used. Hafnium oxidation follows the parabolic rate law, changing with time to the linear one. Oxidation-reaction products are HfO2(moncl) and α-solid solution of oxygen in hafnium. Anomalous oxidation behavior of hafnium having a high impurity content was found in the range 800–950°C. Activation energies for the parabolic and linear oxidation stages were calculated.
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    Molecular and cellular biochemistry 138 (1994), S. 33-37 
    ISSN: 1573-4919
    Keywords: poly(ADP-ribose) polymerase ; structure ; chemistry ; kinetics ; automodification ; mechanism(s)
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract In this minireview, we summarize recent advances on the enzymology of ADP-ribose polymer synthesis. First, a short discussion of the primary structure and cloning of poly(ADP-ribose) polymerase (PARP) [EC 2.4.2.30], the enzyme that catalyzes, the synthesis of poly(ADP-ribose), is presented. A catalytic distinction between the multiple enzymatic activities of PARP is established. The direction of ADP-ribose chain growth as well as the molecular mechanism of the automodification reaction catalyzed by PARP are described. Current approaches to dissect ADP-ribose polymer synthesis into individual reactions of initiation, elongation and branching, as well as a partial mechanistic characterization of the ADP-ribose elongation reaction at he chemical level are also presented. Finally, recent developments in the catalytic characterization of PARP by site-directed mutagensis are also briefly summarized.
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    Molecular and cellular biochemistry 193 (1999), S. 19-22 
    ISSN: 1573-4919
    Keywords: poly(ADP-ribose)polymerase ; kinetics ; allosterism ; regulation
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Here, we describe the latest developments on the mechanistic characterization of poly(ADP-ribose) polymerase (PARP) [EC 2.4.2.30], a DNA-dependent enzyme that catalyzes the synthesis of protein-bound ADP-ribose polymers in eucaryotic chromatin. A detailed kinetic analysis of the automodification reaction of PARP in the presence of nicked dsDNA indicates that protein-poly(ADP-ribosyl)ation probably occurs via a sequential mechanism since enzyme-bound ADP-ribose chains are not reaction intermediates. The multiple enzymatic activities catalyzed by PARP (initiation, elongation, branching and self-modification) are the subject of a very complex regulatory mechanism that may involve allosterism. For instance, while the NAD+ concentration determines the average ADP-ribose polymer size (polymerization reaction), the frequency of DNA strand breaks determines the total number of ADP-ribose chains synthesized (initiation reaction). A general discussion of some of the mechanisms that regulate these multiple catalytic activities of PARP is presented below.
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  • 52
    ISSN: 1573-4943
    Keywords: Alkaline phosphatase ; sodium (2, 2′-bipyridine) oxodiperoxovanadate ; inhibition ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Green crab (Scylla serrata) alkaline phosphatase (EC 3.1.3.1) is a metalloenzyme, which catalyzes the nonspecific hydrolysis of phosphate monoesters. The kinetics of inhibition of the enzyme by sodium (2, 2′-bipyridine) oxodiperoxovanadate, pV(bipy), has been studied. The time course of the hydrolysis of p-nitrophenyl-phosphate catalyzed by the enzyme in the presence of different pV(bipy) concentrations showed that at each pV(bipy) concentration, the rate decreased with increasing time until a straight line was approached, the straight line slopes are the same for all concentrations. The results suggest that the inhibition of the enzyme by pV(bipy) is a slow, reversible reaction with fractional remaining activity. The microscopic rate constants are determined for the reaction of inhibitor with the enzyme.
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    Journal of sol gel science and technology 15 (1999), S. 129-136 
    ISSN: 1573-4846
    Keywords: simulation ; percolation ; aggregation ; structure ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Three-dimensional (3D) Monte Carlo simulations of diffusion limited cluster aggregation at different concentrations (φ) show a crossover from a flocculation regime at short times to a percolation regime close to the gel time (tg). Contrary to suggestions in the literature tg is independent of the system size (L) for large L. The structural and temporal crossovers between flocculation and percolation take place at characteristic values of the cluster mass (mc) and the time (tc) which depend on φ. After normalisation by these characteristic values the crossovers are independent of φ except for very small clusters and at short times. The concentration dependence of mc and tc indicates that the crossover takes place at a given cumulated volume fraction of the clusters independent of φ. At low concentrations the φ-dependence of tg is determined by the cluster growth in the flocculation regime.
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    Journal of sol gel science and technology 2 (1994), S. 35-41 
    ISSN: 1573-4846
    Keywords: carboxylic acids ; mechanism ; kinetics ; ultrafine porosity ; CO2 adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new means for generating silica gel has been developed. Simple two component systems comprising tetraalkoxysilanes and strong carboxylic acids such as formic acid can react rapidly to give transparent monolithic gels. The acid serves as solvent, water source, and catalyst for both hydrolysis and condensation. Water need not be present as an initial reactant; it is generated in situ during the reaction. The gelation reaction is at least two orders of magnitude faster than those conducted in conventional acid-catalyzed aqueous systems at comparable pH*. Kinetic evidence indicates a lowering of the activation energy of condensation reactions, believed to be associated with reaction of silyl carboxylates and silanol groups. Physical properties of the dry gels such as bulk density more closely resemble conventional acid-catalyzed gels than those associated with other rapidly gelling systems. Dry gels often exhibit porosity so fine that nitrogen (at 77°K) is not absorbed at significant rates. Independent evidence of porosity arises from comparison of skeletal and bulk densities, sample immersion in water and adsorption isotherms of CO2.
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  • 55
    ISSN: 1573-4943
    Keywords: Alkaline phosphatase ; green crab ; inhibition ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The inhibition of alkaline phosphatase from green crab (Scylla serrata) by L-cysteine has been studied. The results show that L-cysteine gives a mixed-type inhibition. The progress-of-substrate-reaction method previously described by Tsou [(1988), Adv. Enzymol. Related Areas Mol. Biol. 61, 391–436] was used to study the inactivation kinetics of the enzyme by L-cysteine. The microscopic rate constants were determined for reaction of the inhibitor with the free enzyme and the enzyme–substrate complex (ES) The results show that inactivation of the enzyme by L-cysteine is a slow, reversible reaction. Comparison of the inactivation rate constants of free enzyme and ES suggests that the presence of the substrate offers marked protection of this enzyme against inactivation by L-cysteine.
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  • 56
    ISSN: 1573-4943
    Keywords: Lactate dehydrogenase ; kinetics ; mutagenesis ; specificity
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The Gin residue at amino acid position 102 ofBacillus stearothermophilus lactate dehydrogenase was replaced with Ser, Thr, Tyr, or Phe to investigate the effect on substrate recognition. The Q102S and Q102T mutant enzymes were found to have a broader range of substrate specificity (measured byk cat/K m) than the wild-type enzyme. However, it is evident that either Ser or Thr at position 102 are of a size able to accommodate a wide variety of substrates in the active site and substrate specificity appears to rely largely on size discrimination in these mutants. The Q102F and Q102Y mutant enzymes have low catalytic efficiency and do not show this relaxed substrate specificity. However, their activities are restored by the presence of an aromatic substrate. All of the enzymes have a very low catalytic efficiency with branched chain aliphatic substrates.
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  • 57
    ISSN: 1573-4994
    Keywords: Na,K-ATPase ; fluorescent inhibitor ; kinetics ; energy transfer
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    Topics: Physics
    Notes: Abstract The interaction between the fluorescent ouabain derivative DEDO and purified renal Na,K-ATPase (isolated from different animal species) is investigated. Equilibrium binding studies provide a pK value of about 7.5 and a stoichoimetric coefficient of 1. Nonmodified ouabain exhibits the same affinity to the rabbit enzyme; the enzyme originating from the other sources binds DEDO 10 times less strongly than ouabain. Kinetic studies indicate that this is the consequence of a 10 times higher dissociation rate constant of the complexes formed with DEDO. The fluorescence emission intensity of DEDO is enhanced, being dependent on the enzyme source. The single decay time of DEDO is 3 ns in the absence and 21 ns in the presence of the rabbit enzyme and 14 ns in the presence of the pig renal enzyme. This result suggests that the fluorophore of DEDO is bound to a very hydrophobic environment of the enzyme. Further characterization of the static fluorescence spectra provides evidence for energy transfer between Trp residues of the enzyme and DEDO. Distance estimations suggest that one or two Trp residues are likely to be located in the proximity of the fluorophore.
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  • 58
    ISSN: 1573-4994
    Keywords: Cytochrome b5 ; site-directed mutagenesis ; kinetics ; fluorescence ; membrane-binding
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Cytochrome b5 binds spontaneously to lipid vescles and also self-associates in aqueous solution. Two mutant proteins have been generated, one has a self-association constant which is less than that of the native protein, while the other has a larger self-association constant. All three proteins have Trp in the membrane-binding domain but as aqueous solutions of these proteins contain differing amounts of monomeric protein, the kinetics of fluorescence enhancement, when the proteins are mixed with lipid vesicles, are complex. Similar complex kinetics are seen when the Trp are quenched by the addition of bromolipid vesicles. The mutant which has Trp 108 and 112 both replaced by Leu does not self-associate and shows monoexponential stopped-flow fluorescence kinetics. Identical rate constants are seen with this mutant for fluorescence enhancement by POPC and fluorescence quenching by three bromolipids with bromines at the 6,7-, 9,10-, and 11,12-positions of thesn-2 acyl chain. This rate constant is only 1% of the calculated collisional rate constant and it is suggested that the reduced rate is caused by a reduction in the number of productive collisions rather than by a slow rate of penetration of the membrane-binding domain into the bilayer.
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  • 59
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    Russian chemical bulletin 43 (1994), S. 1451-1456 
    ISSN: 1573-9171
    Keywords: metal carbonyl clusters ; osmium, ruthenium, alkynes ; kinetics ; catalytic effect of halide ions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The results of kinetic studies on ligand substitution in [M3(CO)11X]− complexes (M = Ru, Os; X = Cl, Br, I) are summarized. The [Os3(CO)11X]− complexes react with PPh3 under mild conditions to initially yield monosubstituted products [Os3(CO)10(PPh3)X]−. The rate of CO substitution obeys a first-order equation with respect to the concentration of the complex and does not depend on the ligand concentration. The rates of the reactions decrease in the order Cl 〉 Br 〉 I withΔH≠ values increasing from 15 to 18 kcal mol−1 and ΔS ≠ values varying from −19 to −13 cal mol−1 K−1. The enhanced reactivities of these complexes as well as the low activation energies and negative activation entropies are discussed in terms of the effects of μ-X bridge formation on the transition state of the reaction. Reactions of PPN[Ru3(CO)11−x (Cl)] (PPN is the bis(triphenylphosphine)iminium cation;x=0, 1) and PPN[Ru3(CO)9(μ3-I)] with alkynes are also reported. The reactivities of alkynes follow the order BuC≡CH ≥ PhC≡CH ≥ EtC≡CEt ≥ PhC≡CPh. The higher rates of the reactions of monosubstituted acetylenes compared with those of their disubstituted analogs are explained by agostic interaction between the metal atom and the C-H bond in the reaction transition state and by steric effects. The results obtained attest that the reaction with alkynes occursvia intermediates containing halide bridges and that μ3-halide complexes are more reactive than μ2-halide complexes.
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  • 60
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    Russian chemical bulletin 43 (1994), S. 1646-1650 
    ISSN: 1573-9171
    Keywords: aromatic amines ; amide ions ; oxidation ; dioxygen ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Amide ions generated from secondary aromatic amines with pK a 〉 21 are readily oxidized by dioxygen in the system KOH+18-crown-6+DMSO at room temperature. It was found that the rate limiting stage of the reaction is the interaction of dioxygen with amide ions. The rate of the reaction is determined by two main factors, varying in opposite directions: the degree of ionization of the amine and the reactivity of the amide ions towards dioxygen.
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  • 61
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    Russian chemical bulletin 43 (1994), S. 368-371 
    ISSN: 1573-9171
    Keywords: kinetics ; solvent dynamics ; radical
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of metallotropy of the 3,6-di-tert-butyl-2-(triphenylstannyl)oxyphenoxyl radical has been studied by ESR. The correlation between chemical exchange time τex, solvent polarity, and longitudinal relaxation time of the solvent corresponds to the model of a process controlled by molecular dynamics. A linear relation between τex and correlation time τc for reorientation movements of the radical is found: τex = α · τc. The coefficient α depends on the dielectric properties of the solvent.
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  • 62
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    Glycoconjugate journal 16 (1999), S. 365-373 
    ISSN: 1573-4986
    Keywords: galectin 3 ; laminin binding ; kinetics ; cooperativity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Galectin 3, a β-galactoside binding protein, contains a C-terminal carbohydrate recognition domain (CRD) and an N-terminal segment including multiple repeats of a proline/tyrosine/glycine-rich motif. Previous work has shown that galectin 3 but not the isolated CRD binds to laminin, a multivalent ligand, with positive cooperativity indicating the formation of multiple interactions although the lectin in solution is monomeric. Using surface plasmon resonance, we find that hamster galectin 3 at sub-µmolar concentrations or its isolated CRD at all concentrations binds to a laminin substratum with similar association (kass; 10 – 30 000 M−1 S−1) and dissociation (kdiss; 0.2 – 0.3 S 1 −1 ) rates and weak affinity (Ka; 1 - 3 X 105 M−1). At higher concentrations of galectin 3 the off rate decreases ten fold leading to increased affinity. Ligation of an N-terminal epitope of galectin 3 with a monoclonal Fab fragment increases association and dissociation rates ten fold. A recombinant protein obtained by deletion of the first 93 N-terminal residues binds to laminin with positive cooperativity and a slowly dissociating fraction (Kdiss; 0.002 S−1) accummulates on the substratum. The data suggest that homophilic interactions between CRD as well as N terminal domains are implicated in galectin 3 aggregation on the substratum leading to positive binding cooperativity.
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  • 63
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    Pharmaceutical research 11 (1994), S. 1325-1329 
    ISSN: 1573-904X
    Keywords: interfacial transfer ; partition coefficients ; side-by-side diffusion cells ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A side-by-side diffusion cell setup has been used to determine the pH 7.4 buffer-octanol interfacial transfer constants for twelve compounds. The compounds are a diverse selection of pharmaceuticals, amino acids, and small organics which covers a log distribution coefficient (K) range of −3 to 2. A model based on the resistance summation approach, which deals explicitly with the various barriers involves in the transport process, was used to derive transfer constants from the transport data for each compound. The model gave constants that were well behaved in a published model describing the correlation of the forward and reverse transfer constants to equilibrium K values (r2 = 0.999). These studies demonstrate the utility of side-by-side diffusion cells for the determination of interfacial transfer constants. This type of setup offers the advantages of controlled interfacial area, measurable hydrodynamic effects, and a commercially available apparatus.
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  • 64
    ISSN: 1573-904X
    Keywords: drug delivery ; emulsion ; entrapping efficiency ; polydimethylsiloxane ; glass beads ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Evaluation of entrapping efficiency is difficult for an o/w emulsion formulation containing a lipophilic oily drug, isocarbacyclin methyl ester (TEI-9090), by commonly employed techniques (dialysis, ultrafiltration, or gel filtration), because of its adsorption to the system materials. Employing this characteristic of TEI-9090, we developed an adsorption technique with polydimethylsiloxane-coated glass beads (PDMS-GB). The assay is based on the quantitative adsorption of unentrapped TEI-9090 to the PDMS-GB. The entrapping efficiency of a 10% soybean oil emulsion containing [3H]TEI-9090 (1 µg/mL) assayed by this method approached 100%. The PDMS-GB assay was performed for the emulsion diluted 100 times with physiological saline at different time intervals after dilution over a period of 24 hr. A plot of [3H]TEI-9090 in the emulsion particles versus time showed rapid release within 1 hr, followed by very slow release, reaching equilibrium. Applying first-order kinetics, the data were found to fit to a biexponential equation over the first hour of release. The terminal release resembled the first-order release of the drug from the phospholipid-rich infranatant, which was separated from the creamy layer by ultracentrifugation of the emulsion and contained 35% [3H]TEI-9090. These results suggest that the drug is released from two components in the emulsion.
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  • 65
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    Pharmaceutical research 11 (1994), S. 72-76 
    ISSN: 1573-904X
    Keywords: interleukin 11 (IL-11) ; recombinant human IL-11 ; degradation ; kinetics ; products ; aspartate–proline cleavage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Recombinant human interleukin 11 (rhIL-11) is a multispectrum cytokine that plays an important role in megakaryocytopoiesis and platelet production. Probing rhIL-11 chemical reactivity in aqueous solution is an important initial step in developing a dosage form for rhIL-11 clinical trials. This report documents rhIL-11 degradation kinetics at 50°C in solutions adjusted to pH 3.0 to 9.5. Stressed samples were analyzed by reverse-phase HPLC and degradation product peaks were isolated for structural characterization. The results show maximal stability in the region pH 6.5 to 7.0. Degradation product identification shows that the major reaction pathway in acidic solution involves peptide cleavage at aspartate133–proline134. In alkaline solution, protein disappearance proceeds via nonspecific loss to container surfaces. Degradation products at alkaline pH have not been identified.
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  • 66
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    Pharmaceutical research 11 (1994), S. 165-170 
    ISSN: 1573-904X
    Keywords: dalvastatin ; hydroxymethylglutaryl coenzyme A (HMG-CoA) reductase inhibitor ; epimerization ; hydrolysis ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In aqueous solutions, dalvastatin (1) undergoes epimerization as well as hydrolysis. The transformation of the drug was studied as a function of pH at 25°C in aqueous solutions containing 20% acetonitrile. At all pH values, first-order plots for the conversion are biphasic, indicating rapid equilibration of 1 with its epimer (2) and slower hydrolysis of 1 to the corresponding β-hydroxy acid (3). Apparent first-order rate constants for the biexponential equation are given as a function of pH. The alkyl–oxygen cleavage of the lactone ring results in the epimerization of 1 to 2, whereas the acyl–oxygen cleavage results in the hydrolysis of 1 to 3. The epimerization is an SN1 reaction reaching an equilibrium of [l] eq/[2] eq = 1.27. The epimerization rate is increased with an increase in the water content of the solvent. The hydrolysis of 1 to 3 is acid and base catalyzed. The hydrolysis is reversible in acidic media and irreversible in neutral and basic media. At pH values greater than 9, the hydrolysis reaction proceeds more rapidly than the epimerization.
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  • 67
    ISSN: 1573-904X
    Keywords: o/w emulsion ; serum ; entrapping efficiency ; kinetics ; SDS
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    Topics: Chemistry and Pharmacology
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  • 68
    ISSN: 1573-904X
    Keywords: protein drug ; denaturation ; aggregation ; kinetics ; Eyring equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Denaturation and aggregation kinetics of Aspergillus oryzae β-galactosidase in solution were studied in order to determine whether the stability of protein drugs can be predicted. Denaturation of β-galactosidase, monitored by measuring enzyme activity, conformed to first-order kinetics, whereas aggregation of the denatured form, monitored by high performance size exclusion chromatography, showed a reaction order higher than 1. Denaturation of β-galactosidase was irreversible and exhibited a biphasic kinetic pattern which could be explained by assuming that two isoenzymes denatured irreversibly at different rates. Linear Arrhenius plots were obtained for the estimated rate constants, and ΔH
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  • 69
    ISSN: 1435-1536
    Keywords: Mn(III)-poly(ethylene glycol) ; acrylonitrile ; block copolymerization ; 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 The kinetics and mechanism of thermal polymerization of acrylonitrile initiated by Mn(III) pyrophosphate — poly(ethylene glycol) (PEG, molecular weight 6000) redox system in aqueous sulfuric acid medium was studied in the temperature range 30–60°C. The overall rates of polymerization and the disappearance of Mn3+ were determined. The polymerization was initiated by the organic free radical produced from the Mn3+-PEG reaction and the termination was by the metal ions. The rate of polymerization of acrylonitrile was found to be directly proportional to the square of the monomer concentration and first power of PEG concentration, and inversely proportional to the concentration of Mn3+. The rate of manganic ion disappearance was found to be directly proportional to manganic ion concentration and PEG concentration, and independent of the monomer concentration. Based on these observations, a plausible reaction scheme was suggested and suitable kinetic expressions were evaluated.
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  • 70
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    Fish physiology and biochemistry 20 (1999), S. 279-292 
    ISSN: 1573-5168
    Keywords: heat shock proteins ; hsp70 ; kinetics ; in vitro ; salmon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The heat shock protein (hsp) response of juvenile Atlantic salmon, Salmo salar was investigated in isolated tissues subjected to various degrees of thermal shock. Distinct but overlapping arrays of proteins from the major hsp families (hsps 100, 90, 70, 60 and small hsps) were induced in branchial lamellae, hepatic tissue and erythrocytes. The two most prominent proteins induced by heat shock (MW ≅ 65 and 66 kDa) were found to be antigenic homologues of mammalian hsps72/73. A 2.6 kb transcript upregulated by the same conditions hybridized with cDNA probes to both human and salmon hsp70. Branchial lamellae exhibited the greatest degree of thermotolerance and mounted the most significant heat shock response. Moderate thermal shock induced more species of proteins in branchial lamellae than in hepatic tissue or erythrocytes, with the rate of hsp65/66 synthesis increased by as much as five fold. Thermal shock induced hsp65/66 eight fold in erythrocytes. In contrast, hepatic tissue which was least tolerant of thermal shock, lacked the inducible hsp65 and exhibited minimal induction of hsp66. Persistence of hsps was tested in erythrocytes, where elevated levels remained in the cells for at least 48 h after heat shock. The temporal pattern and magnitude of the hsp response in the stenothermal Atlantic salmon differed from that previously reported for eurythermal species. Also notable was the limited hsp response mounted by salmon tissues exposed to sodium arsenite, a known inducer of hsps. The characteristics of the hsp response to thermal shock support the significance of these proteins in adaptation of Atlantic salmon to environmental insult.
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  • 71
    ISSN: 1573-5168
    Keywords: fish ; sea raven ; gluconeogensis ; hepatocytes ; redox ; LDH ; isozymes ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Previous studies have reported very low rates of gluconeogenesis from lactate in sea raven (Hemitripterus americanus) hepatocytes compared to other teleosts studied. This study examines whether hepatic cell redox or lactate dehydrogenase (LDH) characteristics may explain this observation. Sea raven hepatic optimal LDH activities (pyruvate reductase direction) were more than 40 times less compared with rainbow trout liver values (40 vs 1914 μmol·min−1·g−1 protein). The Km(lactate) was 9.24 and 0.86 mM for sea raven and trout hepatic LDH, but the Km(pyruvate) was similar between the two species (0.11 and 0.21 mM, respectively). These results suggested that sea raven liver LDH did not favour lactate use and was more indicative of the mammalian M-isozyme. Gel electrophoresis showed a predominant intermediate isozyme, with a small amount of the M-type LDH. Phosphoenolpyruvate carboxykinase (PEPCK) was localized to the mitochondrial compartment, while there was no apparent mitochondrial glutamate-oxaloacetate transaminase (GOT) activity. No in vitro lactate flux to glucose was found in untreated, 10 mM ethanol-treated, or 3 mM NH4Cl-treated sea raven hepatocytes, although CO2 production from lactate was decreased by ethanol and increased by NH4Cl. These results provide evidence that cell redox does not limit gluconeogenesis from lactate, while low activities and the kinetic characteristics of LDH may partially explain the low lactate gluconeogenesis reported in sea raven hepatocytes.
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  • 72
    ISSN: 1573-5168
    Keywords: fish ; chloride cell ; morphology ; kinetics ; Km ; Jmax ; acid-base
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    Topics: Biology
    Notes: Abstract Marked morphological responses occur in the gills of freshwater rainbow trout in response to experimental acid-base disturbance and these responses play an important role in acid-base correction. Compensated respiratory acidosis induced by 70h exposure to environmental hyperoxia (elevated water PO2) caused a 33% decrease in branchial chloride cell fractional surface area (CCFA). Metabolic alkalosis induced by normoxic recovery (6h) from hyperoxia (72h) caused a 50% increase in CCFA, whereas metabolic alkalosis induced by infusion (19h) of NaHCO3 caused a 70% rise. However, the largest increase (135%) in CCFA was seen in response to infusion (19h) of HCl. NaCl infusion had no effect. A particular goal was to assess the relative importance of changes in CCFA vs. changes in internal substrate (HCO3 −) availability in regulating the activity of the branchial Cl−/HCO3 − exchange system. For each of the experimental treatments, the accompanying blood acid-base status and branchial transport kinetics (Km, Jmax) for Cl− uptake had been determined in earlier studies. In the present study, a positive linear relationship was established between CCFA and JCl− max in individual control fish in the absence of an acid-base disturbance. By reference to this relationship, observed changes in JCl− max during metabolic acid-base disturbances were clearly due to changes in both CCFA and internal substrate levels (plasma [HCO3 −]) with the two factors having approximately equal influence.
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  • 73
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    Journal of bioenergetics and biomembranes 26 (1994), S. 471-485 
    ISSN: 1573-6881
    Keywords: Mitochondria ; transport ; calcium ; metabolic mediator ; kinetics ; calcium pulses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract The identification of intramitochondrial free calcium ([Ca2+ m) as a primary metabolic mediator [see Hansford (this volume) and Gunter, T. E., Gunter, K. K., Sheu, S.-S., and Gavin, C. E. (1994)Am. J. Physiol. 267, C313–C339, for reviews] has emphasized the importance of understanding the characteristics of those mechanisms that control [Ca2+]m. In this review, we attempt to update the descriptions of the mechanisms that mediate the transport of Ca2+ across the mitochondrial inner membrane, emphasizing the energetics of each mechanism. New concepts within this field are reviewed and some older concepts are discussed more completely than in earlier reviews. The mathematical forms of the membrane potential dependence and concentration dependence of the uniporter are interpolated in such a way as to display the convenience of consideringV max to be an explicit function of the membrane potential. Recent evidence for a transient rapid conductance state of the uniporter is discussed. New evidence concerning the energetics and stoichiometries of both Na+-dependent and Na+-independent efflux mechanisms is reviewed. Explicit mathematical expressions are used to describe the energetics of the system and the kinetics of transport via each Ca2+ transport mechanism.
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  • 74
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    Transport in porous media 16 (1994), S. 237-251 
    ISSN: 1573-1634
    Keywords: phosphate ; soil ; adsorption ; leaching ; kinetics ; computer simulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract Effects of flow rate and distance travelled on average mobilities of phosphate in a soil are estimated from breakthrough curves of phosphate at the outlets of small columns of soil, following step increases in the concentration at the inlets. Experimental results are compared with results from a computer simulation model of leached columns of soil. Average mobilities of phosphate in columns of soil, following a step increase in the input concentration, decrease with decreasing rate of flow and with increasing distance travelled and appear to be linearly correlated on a logarithmic scale with both flow rate and distance travelled. An empirical equation, describing these relationships, is fitted to data from leaching experiments at flow rates between 30 and 600 cm/day in ≈ 10 cm long columns of soil. Coefficients are obtained by curve fitting breakthrough curves, calculated with a numerical computer simulation model, to experimental breakthrough curves. The fitted equation enables extrapolation to flow rates and travel distances that are more relevant to a field situation.
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  • 75
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    Colloid & polymer science 272 (1994), S. 1-16 
    ISSN: 1435-1536
    Keywords: Polymer crystallization ; kinetics ; modeling ; POM ; PEEK
    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 The isothermal crystallization of two engineering polymers — POM and PEEK — was studied, both theoretically and experimentally. The experiments were performed by means of differential scanning calorimetry (DSC) and polarized light optical microscopy (OM). Building on previously developed theoretical formalisms (Avrami/Evans, Hillier and Tobin), a new procedure is presented, based on Tobin's model coupled with a modification of Hillier's calculation technique, to accurately describe the kinetics and mechanism of the crystallization of polymers from quiescent melts. First, it is shown that Tobin's model alone, without modification, is more accurate than Avrami/Evans model to describe single-mechanism processes, for a wide range of materials and for longer crystallization times, despite having exactly the same nature and number of parameters (the kinetic, nucleation and growth rate-related, parameterK and the dimensionalityn). Then, Hillier's formalism is modified and combined with Tobin's model, to accurately predict the kinetics of dual mechanism crystallization processes; a clear contrast is drawn with Hillier's Avrami-based, original procedure which uses the same number and nature of parameters, but cannot adequately predict the experimental behavior. The parameter values predicted by the model(s) and procedure presented in this work are all given, are then physically interpreted and, in the case of POM, related to independent morphological observations by polarized light optical microscopy. They are also consistent with electron microscopy observations made by other authors on the detailed morphology of the spherulitic crystallization of polymers.
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  • 76
    ISSN: 1573-0662
    Keywords: atmosphere ; kinetics ; nitrate radical ; monoterpenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The aim of this work is to study the reactivity of some naturally emitted terpenes, 2-carene, sabinene, myrcene, α-phellandrene, d-limonene, terpinolene and γ-terpinene, towards NO3 radical to evaluate the importance of these reactions in the atmosphere and their atmospheric impact. The experiments with these monoterpenes have been carried out under second-order kinetic conditions over the range of temperature 298–433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). This work is the first temperature dependence study for the reactions of the nitrate radical with the above-mentioned monoterpenes. The measured rate constants at 298 K for the reaction of NO3 with such terpenes are as follows: 2-carene, 16.6 ± 1.8, sabinene 10.7 ± 1.6, myrcene 12.8 ± 1.1, α-phellandrene 42 ± 10, d-limonene 9.4 ± 0.9, terpinolene 52 ± 9 and γ-terpinene 24 ± 7, in units of 10-12 cm3 molecule-1 s-1. The proposed Arrhenius expressions, for the reactions of NO3 with 2-carene, sabinene, myrcene and α-phellandrene are, respectively k1 = (1.4 ± 0.7) × 10-12 exp[(741 ± 190/T)] (cm3 molecule-1 s-1), k2=(2.3 ± 1.3) × 10-10 exp[−(940 ± 200/T)] (cm3 molecule-1 s-1), k3 = (2.2 ± 0.2) × 10-12 exp[(523 ± 35/T)] (cm3 molecule1 s-1) and k4 = (1.9 ± 1.3) × 10-9 exp[−(1158 ± 270/T)] (cm3 molecule-1 s-1). A decrease in the rate constants when raising the temperature has also been found for the reaction of d-limonene with NO3 while an increase in the rate constant with temperature has been observed for the reactions of terpinolene and γ-terpinene with NO3. Tropospheric half-lives for these terpenes have been calculated at night and during the day for typical NO3 and OH concentrations showing that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with NO3 radical can be an important, if not dominant, loss process for these naturally emitted organics and for NO3 radicals.
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  • 77
    ISSN: 1573-0662
    Keywords: δ3-carene ; chlorine atoms ; isoprene ; kinetics ; methacrolein and methyl vinyl ketone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10-10, (2.1 ± 0.5) × 10-10, (3.2 ± 0.5) × 10-10, and (4.9 ± 0.5) × 10-10 cm3 molecule-1 s-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and δ3-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.
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  • 78
    ISSN: 1572-8943
    Keywords: adducts ; cobalt complex ; DSC ; kinetics ; nickel complex ; O,O'-dialkyldithiophosphate ; pyridine ; TG-DTG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal behaviour of tri(O,O'-diisopropyldithiophosphate)cobalt(III), Co(dptp)3 and bis (O,O'-diethyldithiophosphate)nickel(II), Ni(detp)2 and its adducts with pyridine, Ni(detp)2(py)2 or 4-methylpyridine, Ni(detp)(mpy)2 in a dynamic nitrogen atmosphere was investigated by TG-DTG and DSC techniques, which showed a medium endothermic peak for the evolution process of pyridine(or 4-methylpyridine) and a strong exothermic peak for that of O,O'-diethyldithiophosphate. The thermal stability and decomposition patterns for these compounds were compared and interpreted in terms of structural features such as bond character and steric effects. The kinetic parameters and mechanisms of every decomposition stage involved for all these complexes were obtained employing the non-isothermal kinetic analysis method suggested by Malek et al., which showed the kinetics mechanism for pyrolysis of pyridine(or 4-methylpyridine) is an S-B empirical model with lower activation energy, while that of O,O'-dialkyldithiophosphate is a diffusion model. These results are in accord with the fact that two ligands are of different type.
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  • 79
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    Journal of thermal analysis and calorimetry 55 (1999), S. 653-659 
    ISSN: 1572-8943
    Keywords: dehydration ; kinetics ; lanthanide complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The 2-amino-4-chlorobenzoates of Y(III), La(III), Pr(III), Sm(III), Gd(III), Dy(III), Tm(III) and Lu(III) were prepared. Their general formula is Ln(C6H3NH2ClCOO)3·H2O. X-ray analysis demonstrated that all the prepared complexes are isostructural. This indicates the same mode of coordination of water and organic ligands throughout the whole series of lanthanide(III) 2-amino-4-chlorobenzoates. The dehydrations of the complexes were studied under non-isothermal conditions in air. From the thermogravimetric data on the dehydrations, the kinetic models best fitting the experimental TG curves were selected. These models suggest that the dehydration is governed by diffusion processes. Kinetic parameters such as the activation energy and pre-exponential factor were calculated by means of the differential and integral methods.
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  • 80
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    Journal of thermal analysis and calorimetry 55 (1999), S. 877-884 
    ISSN: 1572-8943
    Keywords: dehydration ; kinetics ; manganese(II) oxalate dihydrate ; mechanism ; non-isothermal ; TG-DTA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new method was proposed for determining the most probable mechanism function of a solid phase reaction. According to Coats-Redfern's integral equation Eβ→0 was calculated by extrapolating β to zero using a series of TG curves with different heating rates. Similarly, Eα→0 was calculated according to Ozawa's equation. The most probable mechanism function of the solid phase dehydration of manganese(II) oxalate dihydrate was confirmed to be G(α)=(1-α)1/2 by comparing Eα→0 with Eβ→0.
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  • 81
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    Journal of thermal analysis and calorimetry 56 (1999), S. 855-861 
    ISSN: 1572-8943
    Keywords: education ; kinetics ; microscopy ; solid-state reactions ; teaching materials
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In an attempt to show the importance of preparing extensively teaching materials for comprehensive education in thermal analysis at an undergraduate level, the significance of the teaching materials concerning the thermal analysis and kinetics of the solid-state reactions is discussed by reviewing our teaching activities at Hiroshima University. Application of the thermoanalytical techniques to thermal decomposition of basic copper(II) salts is appropriate for an introductory experiment to thermal analysis. Microscopic observations of the textural change during the thermal dehydration of inorganic salt hydrates are suitable for introducing the kinetics of solid-state reactions. A computer practice of drawing the experimental master plot enables students to understand the kinetic theory.
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  • 82
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    Journal of thermal analysis and calorimetry 56 (1999), S. 939-946 
    ISSN: 1572-8943
    Keywords: combustion ; high pressure DSC ; kinetics ; oil shale ; pyrolysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pressurised differential scanning calorimeter (PDSC) has been used to obtain information on the pyrolysis and combustion characteristics of oil shales. Two distinct exothermic peaks were identified in combustion experiments known as low temperature oxidation (LTO) and high temperature oxidation (HTO) reaction regions. The pyrolysis process of all studied oil shale samples showed one exothermic effect at each total pressure studied. Kinetic data were analysed by Roger & Morris and Arrhenius methods and the results are discussed.
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  • 83
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1329-1334 
    ISSN: 1572-8943
    Keywords: cyclodextrin complexes ; dehydration ; kinetics ; TG-DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Hydrated inclusion complexes of the hosts β-CD (CD=cyclodextrin), γ-CD and permethylated β-CD with the guest clofibric acid were analysed by TG and DSC methods to characterise their dehydration behaviours. Activation energies for dehydration of the β- and γ-CD clofibric acid complexes, determined by isothermal thermogravimetry, are significantly lower (∼20-25%) than those for the corresponding uncomplexed hydrated CDs. These data can be reconciled with X-ray structural data which show that H2O molecules in the complexes occupy different crystal sites from those occupied in the parent CDs.
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  • 84
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    Journal of thermal analysis and calorimetry 57 (1999), S. 607-622 
    ISSN: 1572-8943
    Keywords: Cu–3.4 At.% Sb alloy ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of solute segregation to partial dislocations in a Cu–3.4 At.% Sb alloy was studied by using a phenomenological approach with differential scanning calorimetry and isothermal calorimetry. The material, severely deformed by repeated bending, presented an excess of dissociated edge dislocations with a dislocation density amounting to about 8.5·1014 m−2, calculated using a prior model of the authors, together with calorimetric recrystallization trace analysis. The kinetics was found to be ruled by two overlapping mechanisms: diffusion of solute atoms mostly through dislocation pipes in the initial and middle stages of the reaction process, acting together with bulk solute diffusion in these stages and later. Bulk solute diffusion increases as the reaction proceeds, as shown by the increasing values of apparent activation energy in the reaction. The exponent of the Mehl-Johnson-Avrami equation used in the phenomenological description was successfully fitted to a time—temperature-dependent function, increasing in agreement with the apparent activation energy behaviour, as may be expected.
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  • 85
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    Journal of thermal analysis and calorimetry 58 (1999), S. 293-299 
    ISSN: 1572-8943
    Keywords: ENR ; kinetics ; thermal degradation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Epoxidized natural rubbers (ENRs) with different extents of epoxidation (B) were prepared under various reaction conditions. The effects of the amount of H2O2 and the reaction time on B are discussed. The glass transition temperature Tg, the thermal degradation temperature and the activation energy of thermal degradation of the ENRs increase with B. The results indicate that the thermal stability of the ENRs increases with B.
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  • 86
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    Journal of thermal analysis and calorimetry 58 (1999), S. 317-322 
    ISSN: 1572-8943
    Keywords: chrome iron ore ; kinetics ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of direct reduction of artificial chrome iron ore was studied by isothermal and non-isothermal methods. In the initial, middle and final periods, the reaction is controlled by nucleation and growth, a phase boundary reaction, and diffusion, respectively. In the main reaction region, the kinetic equation is 1−(1−α)1/3=kt and the apparent activation energy is 270 kJ mol−1. The kinetic mechanisms found with the isothermal and non-isothermal methods do not differ, and the activation energy values are approximately the same. However, the non-isothermal method can demonstrate the kinetic process completely.
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  • 87
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    Journal of statistical physics 95 (1999), S. 949-979 
    ISSN: 1572-9613
    Keywords: numerical simulations ; interface description ; kinetics ; phase ordering ; relaxation ; dynamical scaling ; model A ; curved surface ; lipid bilayer ; dominant length scale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract An interface description and numerical simulations of model A kinetics are used for the first time to investigate the intrasurface kinetics of phase ordering on corrugated surfaces. Geometrical dynamical equations are derived for the domain interfaces. The dynamics is shown to depend strongly on the local Gaussian curvature of the surface, and can be fundamentally different from that in flat systems: dynamical scaling breaks down despite the persistence of the dominant interfacial undulation mode; growth laws are slower than t 1/2 and even logarithmic; a new very-late-stage regime appears characterized by extremely slow interface motion; finally, the zero-temperature fixed point no longer exists, leading to metastable states. Criteria for the existence of the latter are derived and discussed in the context of more complex systems.
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  • 88
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    Biodegradation 10 (1999), S. 177-191 
    ISSN: 1572-9729
    Keywords: AQUASIM ; biodegradation ; biofilm ; growth ; kinetics ; methane ; modelling ; nitrification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This article discusses the growth of methanotrophic biofilms. Several independent biofilm growths scenarios involving different inocula were examined. Biofilm growth, substrate removal and product formation were monitored throughout the experiments. Based on the oxygen consumption it was concluded that heterotrophs and nitrifiers co-existed with methanotrophs in the biofilm. Heterotrophic biomass grew on soluble polymers formed by the hydrolysis of dead biomass entrapped in the biofilm. Nitrifier populations developed because of the presence of ammonia in the mineral medium. Based on these experimental results, the computer program AQUASIM was used to develop a biological model involving methanotrophs, heterotrophs and nitrifiers. The modelling of six independent growth experiments showed that stoichiometric and kinetic parameters were within the same order of magnitude. Parameter estimation yielded an average maximum growth rate for methanotrophs, μm, of 1.5 ± 0.5 d−1, at 20 °C, a decay rate, bm, of 0.24 ± 0.1 d−1, a half saturation constant, $${\text{K}}_{{\text{S(CH}}_{\text{4}} {\text{)}}} $$ , of 0.06 ± 0.05 mg CH4/L, and a yield coefficient, $$Y_{CH_4 } $$ , of 0.57 ±: 0.04 g X/g CH4. In addition, a sensitivity analysis was performed on this model. It indicated that the most influential parameters were those related to the biofilm (i.e. density; solid-volume fraction; thickness). This suggests that in order to improve the model, further research regarding the biofilm structure and composition is needed.
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    Photosynthesis research 40 (1994), S. 199-206 
    ISSN: 1573-5079
    Keywords: cytochrome bf complex ; electron transfers ; kinetics ; quinol oxidation ; Q-cycle
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    Topics: Biology
    Notes: Abstract The kinetics of oxidation and reduction of P700, plastocyanin, cytochrome f and cytochrome b-563 were studied in a reconstituted system consisting of Photosystem I particles, cytochrome bf complex and plastocyanin, all derived from pea leaf chloroplasts. Decyl plastoquinol was the reductant of the bf complex. Turnovers of the system were initiated by laser flashes. The reaction between oxidised P700 and plastocyanin was non-homogeneous in that a second-order rate coefficient of c. 5×10−7 M−1 s−1 applied to 80% of the P700+ and c. 0.7×107 M−1 s−1 to the remainder. In the presence of bf complex, but without quinol, the electron transfer between cytochrome f and oxidised plastocyanin could be described by a second-order rate coefficient of c. 4×107 M−1 s−1 (forward), and c. 1.6×107 M−1 s−1 (reverse). The equilibrium coefficient was thus 2.5. Unexpectedly, there was little reduction of cytochrome f + or plastocyanin+ by electrons from the Rieske centre. With added quinol, reduction of cytochrome b-563 occurred. Concomitantly, electrons appeared in the oxidised species. It was inferred that either the Rieske centre was not involved in the high-potential chain of electron transfer events, or that, only in the presence of quinol, electrons were quickly passed from the Rieske centre to cytochrome f +. Additionally, the presence of quinol altered the equilibrium coefficient for the cyt f/PC interaction from 2.5 to c. 5. The reaction between quinol and the bf complex was describable by a second-order rate coefficient of about 3×106 M−1 s−1. The pattern of the redox reactions around the bf complex could be simulated in detail with a Q-cycle model as previously found for chloroplasts.
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  • 90
    ISSN: 1573-5079
    Keywords: fluorescence lifetime ; kinetics ; P680+ ; transient absorption spectroscopy ; water splitting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The PS II–LHC II supercomplex is a novel type of oxygen evolving Photosystem II (PS II) core particle that contains the light harvesting complex proteins Lhcb1/2/4/5 in addition to the PS II reaction centre, oxygen evolving complex (OEC) and inner antennae [Hankamer et al. (1997) Eur J Biochem 243: 422–429]. The 33 and 23 kDa extrinsic proteins in these particles have been localised by image analysis of electron micrographs and averaging techniques [Boekema et al. (1998) Eur J Biochem 252: 268–276]. To assay the functionality of the water splitting complex, we compared the single flash P680+ reduction kinetics in these supercomplexes with those of PS II-rich granal stack membranes (BBYs). We found that the P680+ reduction kinetics in PS II–LHC II supercomplexes were indistinguishable from those in BBYs. We also examined a number of PS II core particles lacking the Lhcb components. All of these had different P680+ reduction kinetics, which we attributed to partial loss of OEC function before and during the measurements.
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  • 91
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    Photosynthesis research 60 (1999), S. 247-256 
    ISSN: 1573-5079
    Keywords: irradiance ; kinetics ; method ; photosynthesis ; regulation ; rubisco
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract An in vivo method for the estimation of kinetic parameters of partial reactions of carboxylation of ribulose 1,5-bisphosphate (RuBP) catalyzed by ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) is described. Rubisco in barley, wheat and bean is different in the ability of its active centers to bind RuBP. The rate constant of the formation of the Rubisco-RuBP complex in these plants at 25 °C is 0.414, 0.245 and 0.660 mM-1 s-1, respectively. The rate constant of the reaction of the Rubisco-bound enediol with CO2 does not differ significantly in barley and wheat, and averages 66 mM-1 s-1. Decreased irradiance inhibits Rubisco in two ways: by reducing the concentration of operating catalytic sites and by decreasing the rate constant of binding of RuBP to Rubisco. High concentrations of CO2 inhibit Rubisco by decreasing the concentration of competent carboxylation centers, without any s ignificant influence upon the rate constants of partial reactions.
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  • 92
    ISSN: 1573-3017
    Keywords: rubidium ; cesium ; kinetics ; clearance-volume model ; fish
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract We used a two-compartment, clearance volume-based model to examine rubidium and cesium pharmacokinetics in channel catfish (Ictalurus punctatus) after intravascular administration. We compared the apparent volumes of distribution in the central and peripheral compartments and the intercompartmental and whole-body clearances of both metals at 20.0 °C and 27.5 °C. Biological half-times of Rb were 15 to 16 d at both temperatures, but Cs biological half-times averaged 101 d and 85 d at 20.0 °C and 27.5 °C, respectively (5 to 7 times longer than those of Rb in the same individual). Both the intercompartmental and total body clearances of Rb were also 6 to 7 times greater than those of Cs. The apparent volumes of distribution for Rb in the central compartments were twice those of Cs and remained constant with temperature. The apparent volumes of distribution of both elements in peripheral compartments were large compared with their corresponding central compartments, and decreased by a similar extent with increased temperature. Cesium tissue to blood ratios were greatest for white muscle, with more than 85% of the Cs present in this tissue. Partitioning of Cs in peripheral tissues apparently decreased with increased temperature conditions. Our results indicate that application of pharmacokinetic modeling techniques can enhance studies of radionuclide kinetics by helping to identify rate-limiting processes within individuals that may control uptake and elimination.
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  • 93
    ISSN: 1573-2932
    Keywords: arid-zone soils ; field capacity ; fractionation ; heavy metals ; kinetics ; redistribution ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Solid-phase transformation of added Cd, Cu, Cr, Ni, Pb and Zn, in two arid-zone soils incubated in the field capacity moisture regime for one year, were studied. The heavy metals were fractionated into six empirically defined fractions using a selective sequential dissolution (SSD) protocol optimized for arid-zone soils. Each of these fractions was named based on the major soil component targeted for dissolution during the specific SSD step, but it is not assumed that they are mineralogically and chemically totally specific. The transformations of the metals in the two soils incubated at the field capacity regime were compared with those at the moisture saturation regime (Han and Banin, 1997). An initial fast stage of transformation of the soluble metals from the exchangeable (EXC) fraction to the less labile fractions (the carbonate (CARB) fraction for Cd, Pb, Zn, Ni and Cu, and the organic matter (OM) fraction for Cr, and to some extent Cu and Ni) occurred during the fractionation and within one hour after addition. This was followed by a second stage, involving long-term transformation processes of all metals: added Cd was transferred from the EXC into the CARB fraction; added Cr was transferred from the CARB to the OM fraction and Pb was transferred very slowly to the easily reducible oxide (ERO) fraction. Added Cu, Ni and Zn were transferred from the EXC and CARB fractions into the ERO fraction and to some extent OM and RO fractions. In Part I of this series, we reported that during incubation in the saturated moisture regime, Zn and Ni were transferred mainly into the RO and OM fractions. Cadmium, Cr and Pb underwent the same transformation pathways during the slow long-term process, with slightly different rates, in both water regimes. At low levels of addition, the incubated soils moved over one year towards a distribution similar to that of the native soil. At higher levels, the soils still remained removed from the quasi-equilibrium which characterized the native soil, even at the end of one year of incubation.
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    Hyperfine interactions 119 (1999), S. 11-21 
    ISSN: 1572-9540
    Keywords: exotic atom ; muonic hydrogen ; pionic hydrogen ; cascade ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Recent theoretical and experimental studies of the exotic atoms with Z = 1 are reviewed. An interplay between the atomic internal and external degrees of freedom is essential for a good description of the atomic cascade. The perspective of ab initio cascade calculations is outlined.
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  • 95
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    Reaction kinetics and catalysis letters 66 (1999), S. 265-272 
    ISSN: 1588-2837
    Keywords: Oxygen ; surface ; silver ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different adsorption forms of oxygen on silver are discussed. Four main types of oxygen forming at different temperatures and oxygen pressures have been distinguished. A kinetic model describing the formation and transformations of the oxygen forms and taking into account the surface amorphization has been proposed. Numerical modeling of stationary concentrations using this model gives evidence for a temperature window ΔT=500–800 K, where a quasimolecular oxygen state (E=530.5 eV, Tdes=800–900 K) can exist at high oxygen pressures.
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  • 96
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    Reaction kinetics and catalysis letters 66 (1999), S. 289-295 
    ISSN: 1588-2837
    Keywords: Resorcinol photooxidation ; kinetics ; intermediates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ethanedial, butanoic acid anhydride and trihydroxybenzenes have been determined as intermediates of resorcinol photocatalytic oxidation. The photoreaction rate shows a 1st order dependence on resorcinol concentration. The calculated reaction rate constant is 2.1×10−8 mol dm−3 s−1, which is similar to the rate constant of phenol photocatalytic oxidation on TiO2 reported beore.
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  • 97
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    Reaction kinetics and catalysis letters 66 (1999), S. 55-62 
    ISSN: 1588-2837
    Keywords: Oxidation of sulfides ; kinetics ; higher Co oxide IR ; XPS ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Low-temperature heterogenous oxidation of sulfide ions on a higher Co oxide system in aqueous medium has been studied. The effects of pH, temperature and catalyst amount on the kinetic parameters as well as on the selectivity of the oxidation process were investigated. An oxidation mechanism has been proposed based on the results of kinetic investigations and on the data obtained by IR and XPS spectroscopic studies of Co oxide before and after sulfide ion oxidation.
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  • 98
    ISSN: 1588-2837
    Keywords: Silica ; monodisperse particles ; supramolecular crystallization ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of supramolecular crystallization of concentrated suspensions is three-dimensional and follows the Avrami-Erofeev equation: A=1-exp[-(kt)m], where m=4. The rate constant k is proportional to the probability of the appearance of a crystallization center in unit volume in unit time and the linear crystal growth rate, which is determined experimentally.
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  • 99
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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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