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  • Articles  (187)
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  • 1995-1999  (153)
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  • 1
    Electronic Resource
    Electronic Resource
    Differential capacitance studies of the specific adsorption of thiosulfate on silver (1998)
    Springer
    Journal of applied electrochemistry 28 (1998), S. 993-998 
    Details
    ISSN: 1572-8838
    Keywords: thiosulfate ; silver ; adsorption ; differential capacitance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The differential capacitance of a polycrystalline Ag electrode was measured in a NaClO4 electrolyte containing Na2S2O3 at concentrations ranging from 0.1 to 20mm and at electrode potentials ranging from −0.9 to −0.3V vs SCE. The differential capacitance measurements were analysed to obtain the surface coverage of specifically adsorbed thiosulfate (S2O32−) as a function of both electrode potential and bulk concentration. The various forms for the adsorption isotherm at an electrochemical interface which are commonly employed are reviewed and discussed. The adsorption behaviour is best explained by the formation of image dipoles by the specifically adsorbed ions, whose energetic interactions are then dominated by repulsion of like dipoles. The adsorption data is quantitatively fit to an adsorption isotherm for interacting dipoles, yielding an effective dipole moment of 0.72D for the system S2O32−/Ag.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1003405329562
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  • 2
    Electronic Resource
    Electronic Resource
    Modelling of cyclic voltammograms for two-step metal deposition on an inert electrode with adsorption (1998)
    Springer
    Journal of applied electrochemistry 28 (1998), S. 819-825 
    Details
    ISSN: 1572-8838
    Keywords: adsorption ; experimental design ; metal electrodeposition ; modelling ; voltammetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Chromium deposition on an inert electrode is a complex process. To gain a better understanding of phenomena involved in multistep reactions we have studied such a mechanism and developed Voltasim, a new software that simulates cyclic voltammograms for a two-step metal deposition with adsorption. In addition, Voltasim is suitable for either reversible or quasi-reversible or irreversible reactions. The software was validated with experimental results obtained for the chromium deposition case. Data fitting was achieved using a screening design of experiments involving 12␣parameters.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1003424123260
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  • 3
    Electronic Resource
    Electronic Resource
    Characterization and stability of doped SnO2 anodes (1998)
    Springer
    Journal of applied electrochemistry 28 (1998), S. 607-612 
    Details
    ISSN: 1572-8838
    Keywords: SnO2 anodes ; doping ; high overvoltage anodes ; surface analysis ; oxidation ; water treatment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Doped tin dioxide electrodes have been prepared by a standard spray pyrolysis technique. The electrochemical behaviour of these electrodes has been investigated by cyclic voltammetry in sulphuric acid using the Fe2+/Fe3+ redox couple system as test reaction. Oxygen evolution has been used to study the stability of doped SnO2 electrodes. The SnO2 electrodes doped with antimony and platinum exhibit the highest stability. XPS analysis shows that the oxidation state of Sn, Sb and Pt are +4, +3 and +2, respectively, the probable species being SnO2, Sb2O3 and PtO.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1003250118996
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  • 4
    Electronic Resource
    Electronic Resource
    An integrated flow reactor-membrane filtration system for heterogeneous photocatalysis. Part I: Experiments and modelling of a batch-recirculated photoreactor (1999)
    Springer
    Journal of applied electrochemistry 29 (1999), S. 533-539 
    Details
    ISSN: 1572-8838
    Keywords: adsorption ; dye photooxidation ; titanium dioxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract A two-part study was undertaken to examine the feasibility of combining a batch-recirculated photoreactor with a hollow-fibre membrane based ultrafiltration unit for heterogeneous photocatalysis applications. Methylene Blue (MB) and titanium dioxide (Degussa, P-25) were used as the test substrate and photocatalyst respectively for this study. This paper, which forms Part I of this study, describes the influence of MB concentration, recirculation flow rate, TiO2 dose, solution volume in the reservoir and solution pH on the photocatalytic reaction rate. The dark adsorption of MB on the TiO2 particle surface was also analysed. The combination of the reservoir and the annular reaction vessel could be modelled as a continuous flow stirred tank in series with a plug-flow reactor. This model predicts that the reaction rate should increase with a decrease of solution volume in the reservoir, both in the low and high substrate concentration regimes of the Langmuir–Hinshelwood kinetics formalism. This prediction was borne out by the experimental data for the low concentration regime. Part II of this series will describe experiments and modelling of the UF unit, and the operation of the combined system, respectively.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1026418208733
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  • 5
    Electronic Resource
    Electronic Resource
    3,5-bis(n-Hydroxyphenyl)-4-amino-1,2,4-triazoles and 3,5-bis(n-aminophenyl)-4-amino-1,2,4-triazoles: a new class of corrosion inhibitors for mild steel in 1m HCl medium (1999)
    Springer
    Journal of applied electrochemistry 29 (1999), S. 1073-1078 
    Details
    ISSN: 1572-8838
    Keywords: acidic media ; adsorption ; corrosion inhibitors ; electrochemical impedance spectroscopy ; mild steel ; triazoles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract A new class of corrosion inhibitors, namely, 3,5-bis(n-hydroxyphenyl)-4-amino-1,2,4-triazoles and 3,5-bis(n-aminophenyl)-4-amino-1,2,4-triazoles which have been labelled n-HPAT and n-APAT has been synthesized. The influence of aminotriazoles on the corrosion of mild steel in 1m HCl has been studied using weight loss and electrochemical impedance spectroscopy. Results obtained show that these compounds are very good anodic inhibitors. The adsorption of these aminotriazoles is found to obey Langmuir adsorption isotherm.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1003421111890
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  • 6
    Electronic Resource
    Electronic Resource
    Adsorption of SO2 from Wet Mixtures on Hydrophobic Zeolites (1998)
    Springer
    Adsorption 4 (1998), S. 25-33 
    Details
    ISSN: 1572-8757
    Keywords: hydrophobic zeolites ; breakthrough curves ; adsorption ; binary mixtures ; modeling ; overall mass transfer ; roll-up
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Breakthrough curve measurements of SO2 and water vapor were carried out on a number of selected mordenite and pentasil zeolites from their binary and ternary mixtures with CO2 at 50 and 100°C. SO2 capacities of these samples were found to be significantly reduced by the presence of water. Competitive adsorption led to unusually high overshoot peaks of SO2 breakthrough curves. On the other hand, SO2 was found to displace water on the samples with very high silica to alumina ratio. A linear driving force, isothermal model was used to predict the breakthrough curves. Langmuir and extended Langmuir equilibrium models were used to describe the equilibrium properties of water and SO2, respectively. The overall mass transfer resistance obtained from the model was compared to the values calculated from a simplified biporous adsorbent model to shed some light on the adsorption kinetics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008883219403
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  • 7
    Electronic Resource
    Electronic Resource
    Neural Network Modeling of Adsorption of Binary Vapour Mixtures (1999)
    Springer
    Adsorption 5 (1999), S. 183-192 
    Details
    ISSN: 1572-8757
    Keywords: adsorption ; activated carbon ; neural network ; ideal adsorption solution theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Three neural network models were used for prediction of adsorption equilibria of binary vapour mixtures on an activated carbon. The predictions were compared both with published experimental data and calculated values from the Ideal Adsorption Solution (IAS) model. The neural network was trained using both binary and single component experimental adsorption data. Even for a limited number of data points (about 60) the network models were capable of approximating experimental data very precisely.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008977528474
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  • 8
    Electronic Resource
    Electronic Resource
    Pressure Effects in Adsorption Systems (1999)
    Springer
    Adsorption 5 (1999), S. 261-278 
    Details
    ISSN: 1572-8757
    Keywords: adsorption ; concentrated systems ; pressure transients ; flow transients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A study of the occurrence of large pressure and flow transients when a strongly adsorbed gas is fed to a column which is initially loaded with a lightly adsorbed gas is presented here. Under certain conditions, these transients can cause premature breakthrough and change the shape of the breakthrough curve. This will result in improper estimation of adsorption parameters by the dynamic column loading method and lower apparent adsorption capacity in a full scale unit. A data acquisition system was used to record the pressure and flow transients. An isothermal PDE model developed to study these transients agreed reasonably well with the nonisothermal experimental results. The PDE model predicts that pressure and flow transients will occur during step and pulse~tests conducted to obtain adsorption and mass transfer parameters by the chromatographic method. For instance, lower adsorption capacity will be realized during step tests due to lowering in column pressure. Oscillations were observed when columns are connected in series. The PDE model also predicts these oscillations. Simulations indicate that the extent of oscillations is dependent on the dead volume between columns.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008955828900
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  • 9
    Electronic Resource
    Electronic Resource
    Factors affecting bioleaching kinetics of sulfide ores using acidophilic micro-organisms (1999)
    Springer
    BioMetals 12 (1999), S. 1-10 
    Details
    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
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009228210654
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  • 10
    Electronic Resource
    Electronic Resource
    Mo incorporation in MCM-41 type zeolite (1998)
    Springer
    Catalysis letters 52 (1998), S. 25-29 
    Details
    ISSN: 1572-879X
    Keywords: metallosilicate ; mesoporous ; MCM-41 ; Mo-MCM-41 ; catalysis ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Mo-incorporated MCM-41 has been prepared by direct hydrothermal synthesis. XRD and N2-adsorption measurements showed the characteristics of MCM-41. IR, FT-Raman and UV-VIS DR spectroscopic analyses gave the evidences for the incorporation of Mo in the framework of MCM-41. They are found to be stable and active for cyclohexanol and cyclohexane oxidation reactions with H2O2 as oxidant. Activity of this system has been compared with that of Ti-MCM-41 and molybdena impregnated on pure siliceous MCM-41.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019019403375
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  • 11
    Electronic Resource
    Electronic Resource
    Adsorption and reduction of CO2 on 12-tungstophosphoric and 12-molybdophosphoric acids in the absence of added reductants (1998)
    Springer
    Catalysis letters 52 (1998), S. 163-170 
    Details
    ISSN: 1572-879X
    Keywords: carbon dioxide ; adsorption ; reduction ; dissociation ; 12-tungstophosphoric acid ; 12-molybdophosphoric acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 12-tungstophosphoric and 12-molybdophosphoric acids are capable of sorbing and reducing CO2 without the presence of added reductants. The adsorbed CO2 (physisorbed as CO2) desorbs from the acids and salts at low temperatures (50–200°C). Carbon dioxide also desorbs only from the acids at high temperatures (500–600°C), suggesting the direct or indirect involvement of the protons in the process and the importance of the Keggin unit as well. Raman and DRIFTS results show that the species responsible for the evolution of CO2 (at high temperatures) are carbonaceous in nature. Carbon deposits extract the anionic oxygen atoms from the Keggin units during the high-temperature desorption process. The extraction of anionic oxygen atoms by carbon is confirmed using labeled carbon dioxide. The spectroscopic data imply that carbon exists on the surface as such but, additionally, as either carbon or CO2 bound to the terminal oxygen atoms of the Keggin anion.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019048209735
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  • 12
    Electronic Resource
    Electronic Resource
    IR study of reaction of 2‐butene adsorbed on deuterated ZSM‐5 and mordenite (1998)
    Springer
    Catalysis letters 53 (1998), S. 215-220 
    Details
    ISSN: 1572-879X
    Keywords: FT‐IR ; adsorption ; butene ; ZSM‐5 ; mordenite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Reactions of cis‐ and trans‐2‐butene adsorbed on deuterated ZSM‐5 and mordenite were studied by IR spectroscopy below 300 K. 2‐butene molecules hydrogen‐bonding to Brønsted acid sites (OD) reacted when the temperature was increased above 250 and 230 K on D‐ZSM‐5 and D‐mordenite, respectively. H/D isotope exchange reaction of Brønsted acidic hydroxy groups accompanied the isomerization of cis‐ to trans‐2‐butene, and then dimerization of trans‐2‐butene followed on ZSM‐5, while rapid formation of paraffinic alkoxy groups was dominantly observed on mordenite.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019086712887
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  • 13
    Electronic Resource
    Electronic Resource
    Alkene selectivity enhancement in the oxidation of propane on calcium-based catalysts (1999)
    Springer
    Catalysis letters 59 (1999), S. 67-72 
    Details
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; calcium-based catalysts ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of propane has been investigated in the presence and absence of tetrachloromethane (TCM) on calcium hydroxyapatite (CaHAp), Ca3(PO4)2, CaSO4 and CaO at 723 K. In the absence of TCM, the conversion of C3H8 on CaHAp was 7.7–9.2% during 6 h on-stream while that on Ca3(PO4)2, CaSO4 and CaO was 0.6, 0 and 0.2–0.4%, respectively. The principal products on all catalysts in the absence of TCM were CO and CO2 with small selectivities to C3H6 and C2H4 (both 5–6%) observed on CaHAp. Upon addition of TCM, the selectivity to C3H6 on all catalysts and the conversion of C3H8 on CaSO4 increased while, with increasing time-on-stream, the changes in the conversion and selectivity were dependent upon the nature of the catalysts. XPS and XRD analyses provide evidence for the presence of chlorine in the surface and/or bulk of three of the catalysts, suggesting that chlorinated species on the solids play a role in the selectivity enhancement, but the absence of chlorine from the sulphate demonstrates the dissimilarities of the catalysts in their abilities to sorb and decompose TCM.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019091731368
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  • 14
    Electronic Resource
    Electronic Resource
    Synergistic effects in the oxidation of methane on strontium and lead hydroxyapatites (1999)
    Springer
    Catalysis letters 57 (1999), S. 161-165 
    Details
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; strontium hydroxyapatite ; lead hydroxyapatite ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of methane has been investigated on lead hydroxyapatite (PbHAp), strontium hydroxyapatite (SrHAp) and their binary mixtures at 873 K. PbHAp showed no activity for the oxidation of methane, while SrHAp produced carbon monoxide selectively at 2–4% conversion. On binary mixtures of the hydroxyapatites the conversion of methane and the selectivity to C2 compounds reached values higher than those of the separate constituents of the mixture. With tetrachloromethane in the feed stream a similar synergistic effect was observed with conversions of methane and selectivities to CH3Cl higher on the binary mixtures than those on either SrHAp or PbHAp. The strontium-containing hydroxyapatite appears to play a crucial role in the activation of methane, while the presence of the lead-containing analogue is apparently required for the minimization of undesirable processes involving methyl radicals.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019024421857
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  • 15
    Electronic Resource
    Electronic Resource
    Fischer-Tropsch synthesis over iron catalysts (1990)
    Springer
    Catalysis letters 7 (1990), S. 241-251 
    Details
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; iron based catalysts ; Fe ; Co ; Ru catalysts ; fixed bed reactors ; fluidized bed reactors ; sulfur poisoning ; oxidation ; coke fouling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Because of the decreased profitability of making synthetic fuels, Sasol intends expanding its production of the higher valued chemicals, in particular waxes and olefins. The advantages and disadvantages of using Fe, Co and Ru catalysts are discussed from the point of view of costs, availability, product selectivity, activity and sensitivity to poisons. The loss of activity and selectivity of iron based catalysts in both fixed and fluidized bed reactors is discussed. The main contributing factors are sulfur poisoning, oxidation and coke fouling. In fixed bed reactors sulfur poisoning and “coke” laydown deactivates the front end of the bed while hydrothermal sintering/oxidation deactivates the back end. In fluidized beds the deposition of large amounts of Boudouard carbon doesnot markedly lower the activity. The smaller catalyst particles end up consisting of small iron carbide entities embedded in a matrix of carbon. The larger catalyst particles consist of cores of inert magnetite surrounded by the carbide/carbon matrix. FT reactor development at Sasol is briefly reviewed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00764506
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  • 16
    Electronic Resource
    Electronic Resource
    A new process for acetic acid production by direct oxidation of ethylene (1999)
    Springer
    Catalysis surveys from Japan 3 (1999), S. 55-60 
    Details
    ISSN: 1572-8803
    Keywords: acetic acid ; oxidation ; Pd ; heteropoly acid ; ethylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new process for acetic acid production by direct oxidation of ethylene which was established and commercialized is described. The catalyst system consisting of Pd and heteropoly acid exhibits excellent activity and selectivity. The addition of Se or Te to the catalyst system is effective to suppress the formation of carbon dioxide. This new process is applicable to a plant of a wide range of size corresponding to the local demand. Because this new process produces little waste water, it is very friendly to the environment.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019003230537
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  • 17
    Electronic Resource
    Electronic Resource
    Preparation of metallosilicates with zeolite structure by atom-planting method (1998)
    Springer
    Catalysis surveys from Japan 2 (1998), S. 121-132 
    Details
    ISSN: 1572-8803
    Keywords: zeolite ; metallosilicate ; atom-planting ; modification ; catalysis ; acidity ; shape-selective alkylation ; oxidation ; hydrogen peroxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Atom-planting, a useful method to prepare some metallosilicates having zeolitic structure, was proposed. By treatment of highly siliceous zeolite with metal chloride vapor at selected temperature, metal cation could be introduced into the defect sites (hydroxyl nests) of zeolite framework. By the atom-planting method, some metallosilicates which are difficult to be synthesized by hydrothermal synthesis could be prepared. The vapor phase shape-selective alkylation of ethylbenzene with ethanol, and the liquid phase selective oxidation with hydrogen peroxide on the metallosilicates prepared by atom-planting method were reviewed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019034610065
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  • 18
    Electronic Resource
    Electronic Resource
    Catalysis by porous heteropoly compounds (1998)
    Springer
    Catalysis surveys from Japan 2 (1998), S. 31-44 
    Details
    ISSN: 1572-8803
    Keywords: porous heteropoly compounds ; Pt-promoted heteropoly compounds ; shape selectivity ; water-tolerant catalyst ; hydrogenation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper attempts to review recent works on catalysis of porous heteropoly compounds. The salts of heteropolyacids having Keggin structure with large cations like Cs+ are porous materials. For Cs hydrogen salts, the pore width can be controlled by the Cs content. Cs2.5H0.5PW12O40 has the largest amount of protons on the surface among the acidic Cs salts and possesses pores with bimodal distribution in the micro and meso region. Efficient performances were demonstrated for acid-catalyzed reactions such as skeletal isomerization of η-butane in solid-gas system, alkylation and acylation in solid-liquid system, and hydrolysis and hydration in solid-water system. A microporous salt, Cs2.2H0.8PW12O40, exhibited reactant shape selectivity towards direct decomposition of esters. Furthermore, an ultramicroporous bifunctional catalyst, Pt–Cs2.1H0.9PW12O40 of which the pore width is around 5 Å, exhibits reactant shape selectivity for hydrogenation of alkenes and oxidation of hydrocarbons, and product shape selectivity for skeletal isomerization of η-butane.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019053719634
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  • 19
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    Electronic Resource
    Sorption Equilibria and Kinetics of Hydrocarbons onto Activated Carbon Samples Having Different Micropore Size Distributions (1999)
    Springer
    Adsorption 5 (1999), S. 25-37 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1026481704926
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  • 20
    Electronic Resource
    Electronic Resource
    Propane and oxygen action on NOx adspecies on low-exchanged Cu-ZSM-5 (1998)
    Springer
    Catalysis letters 51 (1998), S. 27-40 
    Details
    ISSN: 1572-879X
    Keywords: NO ; adsorption ; Cu-ZSM-5 ; TPD ; nitrosopropane ; N2O
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A surface intermediate with a C/N ratio close to 3 has been shown by TPD to form at co-adsorption of NO and propane as well as NO, propane and O2 on low-exchanged Cu-ZSM-5. The adsorption of NO, propane and oxygen has been studied to evaluate their effect on the formation of this complex. Its formation is accompanied by a decrease in the concentration of surface nitrite–nitrate. The kinetics of nitrite–nitrate adspecies formation as a function of the reagents concentration and temperature has been investigated. Some NO adspecies have been found to decompose yielding N2O.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019024715245
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  • 21
    Electronic Resource
    Electronic Resource
    Density functional theory (DFT) and microcalorimetric investigations of CO adsorption on Pt clusters (1998)
    Springer
    Catalysis letters 51 (1998), S. 139-147 
    Details
    ISSN: 1572-879X
    Keywords: microcalorimetry ; carbon monoxide ; adsorption ; platinum ; DFT
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Microcalorimetric measurements were conducted at 573 K of CO adsorption on Pt clusters supported in L-zeolite. The measured heat of CO adsorption is 175 kJ/mol, and the heat decreases to 90 kJ/mol near saturation coverage. Quantum chemical calculations were performed using density functional theory to study the interaction of CO with 10-atom Pt clusters. The heat of CO adsorption on atop-sites is calculated to be 209 kJ/mol, while a lower heat of 142 kJ/mol is calculated for CO on bridge-sites. These values decrease to 197 and 102 kJ/mol for population of two atop-sites and two bridge-sites, respectively, on the same Pt10 cluster. The heat of adsorption decreases to 157 kJ/mol when six CO molecules adsorb on six atop-sites of the cluster. The calculated initial heat of CO adsorption on Pt10 clusters is in agreement with experimental and theoretical values reported for CO adsorption on Pt single-crystal surfaces. The higher heat of CO adsorption at atop-sites may be caused by more σ-donation from CO to sp orbitals of Pt for atop-sites. The heat of CO adsorption on bridge-sites becomes higher on negatively charged platinum clusters. The calculated C-O stretching frequencies for charged and neutral platinum clusters agree with experimental data.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019038512945
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  • 22
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    Partial oxidation of propene over metal oxide catalysts pretreated with NO2 (1998)
    Springer
    Catalysis letters 53 (1998), S. 73-76 
    Details
    ISSN: 1572-879X
    Keywords: nitrogen dioxide ; titania ; propene ; selective oxidation ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Titania pretreated with NO2 has been found to catalyze the partial oxidation of propene into oxygenates such as acetone and acrolein at around 623 K, while fresh TiO2 produces only carbon oxides. Temperature‐programmed desorption (TPD) revealed that nitrogen oxides adsorbed on TiO2 are stable at temperatures below 673 K. Even after the propene oxidation at 573 K for 2 h, nitrogen oxides were confirmed still to exist on the TiO2 surface. At temperatures higher than 673 K, however, the desorption and/or the reduction of the adsorbed nitrogen oxides took place, and concomitantly the catalytic ability giving oxygenates disappeared.
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    Platinum deactivation: in situ EXAFS during aqueous alcohol oxidation reaction (1998)
    Springer
    Catalysis letters 55 (1998), S. 141-145 
    Details
    ISSN: 1572-879X
    Keywords: platinum ; EXAFS ; catalysis ; catalyst deactivation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract With a new set‐up for in situ EXAFS spectroscopy the state of a carbon‐supported platinum catalyst during aqueous alcohol oxidation has been observed. The catalyst deactivation during platinum‐catalysed cyclohexanol oxidation is caused by platinum surface oxide formation. The detected Pt–O co‐ordination at 2.10 Å during exposure to nitrogen‐saturated cyclohexanol solution is different from what is observed for the pure oxidised platinum surface (2.06 Å).
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    URL: http://dx.doi.org/10.1023/A:1019007601442
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    Insights into surface reactivity: formic acid oxidation on Cu(110) studied using STM and a molecular beam reactor (1998)
    Springer
    Catalysis letters 56 (1998), S. 77-83 
    Details
    ISSN: 1572-879X
    Keywords: catalysis ; combustion ; oxidation ; formic acid ; STM ; molecular beams ; surface diffusion ; surface reactivity ; active sites ; reconstruction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Using a combination of STM and molecular beam reactor data we summarise some important features of a model reaction (formic acid oxidation on Cu(110)) which is of general significance to surface reactivity and to catalysis. Three such features are highlighted here. The first concerns the role of weakly held species (possibly physisorbed) in surface reactions. These species, although of very short lifetime on the surface, can, nevertheless, diffuse over long distances to “find” a sparse distribution of active sites. Thus a very low coverage of oxygen on the surface of Cu(110) increases the sticking probability of all the formic acid molecules which strike the surface to high value (0.82), even though the clean surface is relatively unreactive. The important concept here is the “diffusion circle” or “collection zone” which represents the area of surface visited by the molecule in its short sojourn in the weakly held state. The second theme concerns the concept of the “flexible surface”. We show that the involvement of surface atoms in reactions directs the structure and reactivity for a particular reaction. For formic acid oxidation the liberation of Cu atoms during the removal of oxygen as water leads to gross restructuring of the surface and can lead to “compression” of one reactant (the oxygen in this case) into a lower area, higher local coverage, unreactive state (the c(6×2) oxygen structure). Thirdly, and finally, it is proposed that, for many surface reactions, the surface acts in an analogous way to a solvent, supporting a “dissolved” (highly mobile and fluxional) phase of intermediates at low coverage, which crystallise out above a critical coverage (the 2D “solubility limit”).
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    URL: http://dx.doi.org/10.1023/A:1019021431910
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    A study of “superacidic” MoO3/ZrO2 catalysts for methane oxidation (1999)
    Springer
    Catalysis letters 57 (1999), S. 109-113 
    Details
    ISSN: 1572-879X
    Keywords: superacid ; zirconia ; molybdenum oxide ; methane ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of zirconia-supported molybdenum oxide catalysts with different molybdenum loadings prepared using conditions reported to generate “superacidity” have been evaluated for their performance as catalysts for methane oxidation. A marked dependence of Mo content on activity has been observed, with the most active material being that with intermediate molybdenum content. 5 wt% MoO3/ZrO2 compares favourably with ZrxCe1-xO2 for methane combustion. The presence of MoO3 is observed to stabilise the tetragonal polymorph of ZrO2 and, as Mo content is increased, dispersed MoO3 crystallites are formed as evidenced by Raman spectroscopy. Temperature-programmed reduction studies evidence differences in the reduction behaviour of the materials as a function of loading. The results indicate that molybdenum oxide supported on monoclinic zirconia gives rise to the most active catalyst. It is tentatively suggested that the formation of a MoO3 monolayer during reaction may be of importance.
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    FTIR spectroscopic evidence of formation of geminal dinitrogen species during the low-temperature N2 adsorption on NaY zeolites (1999)
    Springer
    Catalysis letters 58 (1999), S. 21-26 
    Details
    ISSN: 1572-879X
    Keywords: adsorption ; adsorption isotherms ; dinitrogen ; FTIR spectroscopy ; geminal species ; NaY ; nitrogen ; zeolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Adsorption of N2 on NaY zeolites at 85 K and equilibrium pressures higher than 1 kPa results in the formation of geminal dinitrogen complexes characterized by an IR band at 2333.5 cm−1 (2255.4 cm−1 after adsorption of 15N2). With decreasing equilibrium pressure the complexes tend to loose one N2 ligand, thus forming linear species characterized by an IR band at 2336.8 cm−1 (2258.7 cm−1 after adsorption of 15N2). All species disappear completely after evacuation. Co-adsorption of N2 and CO revealed that the dinitrogen complexes are formed on Na+ cations. The changes in the concentrations of the linear and geminal N2 species with the changes in the equilibrium pressure are excellently described by equations of adsorption isotherms proposed earlier for mono- and di-carbonyls.
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    URL: http://dx.doi.org/10.1023/A:1019040825491
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    The detailed kinetics of the adsorption of hydrogen on polycrystalline copper studied by reactive frontal chromatography (1999)
    Springer
    Catalysis letters 59 (1999), S. 151-155 
    Details
    ISSN: 1572-879X
    Keywords: hydrogen ; copper ; activation energy ; adsorption ; sticking probability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The coverage-dependent sticking probabilities of molecular hydrogen on polycrystalline copper supported on alumina have been determined in the temperature range 213–273 K by analysis of the hydrogen frontal adsorption line shape. In this temperature range the initial sticking probabilities increase from 8× 10−13 (213 K) to 1.3× 10−10 (273 K). The overall activation energy to adsorption has been found to be 42 kJ mol−1. The application of reactive frontal chromatography for the measurement of hydrogen sticking probabilities on copper is a novel variant of the N2O reactive frontal chromatographic method, developed for the measurement of copper surface areas. Its use here shows that reactive frontal chromatography may be applied generally to any adsorbate/adsorbent system involving activated adsorption and low sticking probabilities.
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    URL: http://dx.doi.org/10.1023/A:1019028806778
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    Partial oxidation of methane to synthesis gas (1990)
    Springer
    Catalysis letters 6 (1990), S. 181-186 
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    ISSN: 1572-879X
    Keywords: Metals for catalysis “syngas” ; oxidation ; nickel ; platinum group metals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Partial oxidation of methane to synthesis gas has been carried out over a number of transition metal catalysts under a range of conditions. It is found that the metals Ni, Ru, Rh, Pd, Ir and Pt, either supported on alumina or present in mixed metal oxide precursors, will bring the system to equilibrium. The yield of CO and H2 improves with increasing temperature in the range 650–1050 K, and decreases with increasing pressure between 1 and 20 atm. An excellent yield (∼92%) is obtained with a 4∶2∶1 N2∶CH4∶O2 ratio at 1050 K and atmospheric pressure, with a space velocity of 4×104 hour−1.
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    URL: http://dx.doi.org/10.1007/BF00774718
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    Ethylene adsorption on Pt/Au/SiO2 catalysts (1999)
    Springer
    Catalysis letters 60 (1999), S. 1-9 
    Details
    ISSN: 1572-879X
    Keywords: microcalorimetry ; IR ; platinum ; gold ; ethylene ; CO ; adsorption ; quantum chemical calculations ; DFT
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ethylene adsorption on a Pt/Au/SiO2 catalyst (2 wt% Pt; Au/Pt atomic ratio of 10) was studied using adsorption microcalorimetry and FTIR spectroscopy. Ethylene adsorption at 300 K on Pt/Au/SiO2 produced π‐bonded, di‐σ‐bonded, and ethylidyne species with an initial heat of 140 kJ/mol, compared to a heat of 157 kJ/mol for Pt/SiO2 on which only ethylidyne species formed. At 203 and 263 K, ethylene adsorbed on Pt as well as on Au surface atoms for the Pt/Au/SiO2 catalyst. Quantum chemical, DFT calculations indicate that Au exerts a significantly smaller electronic effect on Pt than does addition of Sn to Pt.
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    URL: http://dx.doi.org/10.1023/A:1019038503569
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    Prospects for detecting metal–adsorbate vibrations by sum‐frequency spectroscopy (1999)
    Springer
    Catalysis letters 61 (1999), S. 7-13 
    Details
    ISSN: 1572-879X
    Keywords: sum‐frequency spectroscopy ; Pt(111) ; carbon monoxide ; adsorption ; far‐infrared ; free‐electron laser
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Sum‐frequency spectroscopy (SFS) was used in an attempt to detect the platinum–carbon vibration of CO adsorbed on Pt(111). The international free‐electron laser FELIX at the FOM Institute, Rijnhuizen, provided the required tunable far‐infrared (19–23 µm) source, while complementary measurements in the C–O stretch region (4.7–5.1 µm) were performed at the University of Oxford with a conventional nanosecond laser system. Ordered Pt(111) surfaces were prepared by the H2/O2 flame annealing approach and CO monolayers were produced by exposure of the Pt crystal to gaseous CO in a flow reactor. The monolayers were characterized by sum‐frequency (SF) measurements of the v C-O vibrational frequency. The CO adsorbed primarily in the terminal (atop) configuration, with a v C-O frequency of around 2078 cm−1. In the far‐IR region, the non‐resonant background from the Pt substrate could readily be detected by SFS, but there was no evidence for the v Pt-CO mode. Direct laser‐induced desorption and thermal desorption of CO are unlikely under the experimental conditions. It is therefore probable that the intrinsic cross‐section of the Pt–CO mode is too low for easy detection by SFS. The implications for the use of SFS to detect metal–adsorbate vibrational modes are discussed in light of these findings.
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    Effect of water on the reduction of NOx with propane on Fe‐ZSM‐5. An FTIR mechanistic study (1999)
    Springer
    Catalysis letters 62 (1999), S. 35-40 
    Details
    ISSN: 1572-879X
    Keywords: Fe‐ZSM‐5 ; carbon monoxide ; FTIR spectroscopy ; nitrates ; nitrogen monoxide ; selective catalytic reduction ; adsorption ; zeolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Adsorption of NO on Fe‐ZSM‐5 leads to formation of Fen+–NO (n = 2 or 3) species (1880 cm-1), Fe2+(NO)2 complexes (1920 and 1835 cm-1) and NO+ (2133 cm-1). Water strongly suppresses the formation of NO+ and Fen+(NO)2 and more slightly the formation of Fen+ –NO. Introduction of oxygen to NO converts the nitrosyls into surface nitrates (1620 and 1575 cm-1) and this process is almost unaffected by water. The nitrates are thermally stable up to ca. 300°C, but readily interact with propane at 200°C, thus forming surface C–H–N–O deposit (bands in the 1700–1300 cm-1 region). Here again, water does not hinder the process. The C–H–N–O deposit is relatively inert (it does not interact with NO or NO + O2 at ambient temperature) but, at temperatures higher than 250 °C, it is decomposed to NCO- species (bands at 2215 (Fe–NCO) and 2256 cm-1 (Al–NCO)). In the presence of water, however, the Fe–NCO species only are formed. At ambient temperature the NCO- species are inert towards NO and O2, but easily react with a NO + O2 mixture. The mechanism of the selective catalytic reduction of nitrogen oxides on Fe‐ZSM‐5 and the effect of water on the process are discussed.
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    A Study of Adsorption of Water Vapour on Wool under Static and Dynamic Conditions (1998)
    Springer
    Adsorption 4 (1998), S. 63-73 
    Details
    ISSN: 1572-8757
    Keywords: wool ; water vapour ; adsorption ; diffusion ; column dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption of water vapour on wool provides not only textile comfort, but also convenience in transportation due to increase in its bulk density. The adsorption and desorption isotherms of water vapour for wool were determined by both volumetric technique using a Coulter Omnisorp 100CX instrument and gravimetric method employing a Cahn 2000 electronic microbalance. Adsorption isotherm fitting to B.E.T. model and hysteresis on desorption was observed. The average effective diffusion coefficient of water in wool was found to be 8.4 × 10-14 m2s-1 at 25°C from gravimetric data. The effects of packing height and air velocity on the breakthrough curves were also investigated in the wool packed columns. For pseudo first order model, k values changing between 0.33 × 10-6 − 69 × 10-6 s-1 was obtained for 2.2–6.4 cm s-1 air velocity and 0.05–0.20 m packing height ranges.
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    Effects of Surface Oxygen of Activated Carbon on Alkaloid Adsorption: A Molecular Dynamics Simulation Study (1999)
    Springer
    Adsorption 5 (1999), S. 97-108 
    Details
    ISSN: 1572-8757
    Keywords: adsorption ; molecular simulation ; activated carbon ; surface oxygen ; alkaloids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The influence of the density and the type of surface oxygen on the adsorption of berberine alkaloid onto activated carbon was investigated using the molecular dynamics simulation method in vacuum. The carbon surface consisted of a basal plane of graphite and surface oxygen groups which were bonded on the graphite plane in a regular square array with various densities. Two types of surface oxygen groups, =O and —OH, were employed. The simulation results showed that the berberine alkaloids were favorable to be adsorbed on the negative charged carbon surfaces. It was indicated that the vdw attraction of the carbon surface to the alkaloid molecule dominates the adsorption only at the lower surface density of oxygen. It is also indicated that a good adsorptive selectivity for a certain berberine alkaloid can be obtained by controlling the density of surface oxygen. The adsorption simulation of berberine alkaloids onto activated carbon in the presence of water was also carried out by using a dome-shape molecular model for presenting the alkaloid/water/carbon system. It was found that the adsorption of berberine alkaloids on the activated carbon which has a higher density of surface oxygen was strongly inhibited by the presence of water.
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    Pure and Binary Gas Adsorption Equilibria and Kinetics of Methane and Nitrogen on 4A Zeolite by Isotope Exchange Technique (1999)
    Springer
    Adsorption 5 (1999), S. 145-158 
    Details
    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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    Impedance Spectroscopic Measurements of Pure Gas Adsorption Equilibria on Zeolites (1999)
    Springer
    Adsorption 5 (1999), S. 159-167 
    Details
    ISSN: 1572-8757
    Keywords: impedance spectroscopy ; uptake curve ; adsorption ; polarization of adsorbate ; dielectric properties of adsorbed phases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Physisorption equilibria of gases on inert porous solids like activated carbon or molecular sieves can be characterized by measuring the (frequency dependent) capacitance of a capacitor filled with a sample adsorbent. This quantity strongly depends not only on the physico-chemical structure of the empty adsorbent in vacuum, but also on the permanent or induced dipole moments of the molecules adsorbed and of the fluid phase. Consequently, it should be possible to determine the excess mass being adsorbed on the internal surface of a highly porous solid by measurements of the dielectric constant. The aim of this work is to show for various pure gases and adsorbents that the change of the capacitance of an adsorption system depends on the adsorbed mass. Therefore, this effect can be used to characterize porous solids and their adsorbates and, for example, to check the state or the quality of industrial adsorbents during a process on site if calibration measurements have been taken (Staudt et al., 1994, 1998).
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    Liquid Phase Separation of Polar Hydrocarbons from Light Aromatics Using Zeolites (1999)
    Springer
    Adsorption 5 (1999), S. 399-407 
    Details
    ISSN: 1572-8757
    Keywords: zeolites ; polar compounds ; adsorption ; adsorption isotherms ; equilibrium ; liquid phase ; breakthrough curves ; acetonitrile ; acrylonitrile ; dioxane ; ZSM-5 ; MCM-22 ; Na-X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The liquid phase removal of low concentrations of polar compounds (acetonitrile, acrylonitrile and dioxane) from toluene by adsorption on zeolites reveals very high selectivity factors. Kinetic selectivity factors as high as 16,100 are observed. The selection of the zeolites (MFI, MWW and FAU type) allowed the study of the effects of varying aluminum content, the presence and absence of acidic centers and varying pore volumes. To assess the relative effectiveness of each adsorbent, both equilibrium and continuous flow, pseudo equilibrium, breakthrough experiments were conducted. The continuous flow experiments were carried out at 25 and 75°C. The zeolites H-ZSM-5, H-MCM-22 and Na-X are highly effective in removing the polar compounds from toluene to a concentration level down to less than 20 ppm (detection limit). The results obtained with the equilibrium batch experiments are confirmed by the continuous flow breakthrough experiments.
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    Kinetics of the gas-solid heterogeneous photocatalytic oxidation of trichloroethylene by near UV illuminated titanium dioxide (1990)
    Springer
    Catalysis letters 4 (1990), S. 345-354 
    Details
    ISSN: 1572-879X
    Keywords: Ultraviolet heterogeneous photocatalysis ; oxidation ; trichloroethylene ; titania ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetics of the gas/solid heterogeneous photocatalytic oxidation of dilute trichloroethylene (TCE) vapors by ultraviolet-illuminated titanium dioxide have been determined using a fixed-bed dynamic photoreactor. Reaction rate dependences on inlet TCE, oxygen and water vapor concentrations were found to consist of both reactant sensitive and insensitive regions. In the reactant sensitive regions, measured limiting apparent reaction rate orders for TCE, oxygen and water vapor are 0.8, 1.7 and — 3, respectively. Water vapor in the reactant stream lowersinitial reaction rates relative to corresponding water free conditions, but is required to sustain photocatalytic activity for extended periods of time.
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    The preparation and characterisation of nanometre platinum colloids on silicon wafers as model catalysts (1998)
    Springer
    Catalysis letters 50 (1998), S. 49-57 
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    ISSN: 1572-879X
    Keywords: model catalysts ; spin coating ; Pt colloid ; AFM ; XPS ; Si wafer ; particle size ; oxidation ; reduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Platinum particles of 2 nm diameter have been immobilised on oxidised silicon wafers by spin coating with colloidal solutions and characterised by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The coverage and dispersion of the Pt colloids on the Si wafer are controlled by varying the concentration and the spin speed. Under optimal conditions mono-dispersed Pt colloids on silicon wafers are prepared. For the Pt colloids immobilised on the Si wafer, the majority of the stabilising ligands are removed through a reduction (with H2 at 200°C) or an oxidation (in air at 300°C) procedure. AFM showed that particle sizes are retained after the reduction procedure, while significant sintering occurs after oxidation. The mechanism of ligand removal was studied using an in situ XPS reaction cell.
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    The CO2–CeO2 interaction and its role in the CeO2 reactivity (1998)
    Springer
    Catalysis letters 56 (1998), S. 199-202 
    Details
    ISSN: 1572-879X
    Keywords: cerium ; gas carbonic ; propane ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The interaction between CO2 and CeO2 and its role in the surface reactivity of alumina-supported cerium oxide has been studied by programmed thermodesorption (TPD) of CO2 and FTIR spectroscopy. The performance of Ce/Al2O3 systems was then analyzed for the propane oxidation in presence of CO2. The results have shown that the catalytic activity decreased when carbonate species are formed at the surface of CeO2. This behavior was attributed to the presence of CO2 from three different sources: contamination before use, during the handling of the samples, contamination proceeding from the reactants and from CO2 produced by the reaction itself.
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    A new strategy for alkane oxidation with O2 using N‐hydroxyphthalimide (NHPI) as a radical catalyst (1999)
    Springer
    Catalysis surveys from Japan 3 (1999), S. 27-35 
    Details
    ISSN: 1572-8803
    Keywords: oxidation ; oxygen ; alkane ; N‐hydroxyphthalimide ; radical catalyst
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A practical catalytic method to convert alkanes into the corresponding oxygen‐containing compounds with O2 under mild conditions using N‐hydroxyphthalimide (NHPI) in the presence or absence of a transition metal was developed. Thus, cyclohexane was successfully converted into adipic acid in good conversion and selectivity by a combined catalytic system consisting of NHPI and Mn(acac)2. Lower alkane such as isobutane was converted into t‐butyl alcohol (83%) under 10 atm of air by NHPI‐Co(OAc)2 system. Alkylbenzene such as toluene was oxidized to benzoic acid in high yield (81%) under normal temperature and pressure of dioxygen in the presence of a catalytic amount of NHPI and Co(OAc)2. ESR measurements showed that phthalimide‐N‐oxyl generated from NHPI under dioxygen atmosphere is a key species in this oxidation and functions as a radical catalyst.
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    Electrochemical oxidation of a carbon black loaded polymer electrode in aqueous electrolytes (1999)
    Springer
    Journal of solid state electrochemistry 3 (1999), S. 179-186 
    Details
    ISSN: 1433-0768
    Keywords: Key words Cathodic protection system ; Carbon ; oxidation ; Composite carbon/polymer anode ; Lifetime
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The suitability of a polymeric composite material for use as part of an anode structure in a cathodic protection system has been examined. The composite material was a conductive blend (volume resistivity typically 1.5 Ω cm) of carbon black in a polyethylene binder. A long operational lifetime for the material demands that the rate of carbon loss must be low. In the work reported here, electrochemical and in situ analytical techniques were employed to characterise the performance of the material over a wide range of anodic current densities in a variety of aqueous electrolytes. The predominant anodic electrochemical reaction on the polymeric material is CO2 formation in acid and neutral solutions, which causes loss of carbon from the surface and the development of a non-conducting layer of polyethylene. The characteristics of the reaction suggest that it occurs via the discharge of H2O. In alkaline pH, however, the anodic reactions are more complex. A high OH− concentration (pH 12 or higher) favours the formation of oxygen rather than CO2, particularly at low anodic potentials. The presence of CO3 2− in the electrolyte catalyses the evolution of oxygen at pH values as low as 9. The electrochemical formation of oxygen always occurs in parallel with the generation of some humic acid in the solution.
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    URL: http://dx.doi.org/10.1007/s100080050145
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    Estimation of mercaptans with 1-chlorobenzotriazole (1990)
    Springer
    Microchimica acta 102 (1990), S. 271-276 
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    ISSN: 1436-5073
    Keywords: mercaptans ; oxidation ; disulphide ; Chlorobenzotriazole ; potentiometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A simple but accurate potentiometric method for the estimations of mercaptans in 0.01M perchloric acid has been developed, based on their oxidation with 1-Chlorobenzotriazole. Quantitative oxidation solely to the disulphide stage is ensured by using critical amounts of methanol, acetonitrile and potassium iodide. Chloride, mercury(II) and copper(II) interfere. A back-titration procedure can also be used. The oxidation products have been identified.
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    Secondary ion emission of selected transition metals under nitrogen oxides (1990)
    Springer
    Microchimica acta 102 (1990), S. 71-78 
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    ISSN: 1436-5073
    Keywords: SIMS ; DSIMS ; transition metals ; nitrogen oxides ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The emission of various positive secondary ions has been investigated for polycrystalline targets of Ti, V, Cr, Nb, Ta, Co, Ni, Cu, Pd and Pt, which were bombarded by Ar+ ions under “dynamic” SIMS (DSIMS) conditions in the presence of the gaseous nitrogen oxides N2O, NO and NO2 at fixed pressure and under residual gas. Besides ions of the Me+ type several fragmentary ions (e.g. N+, O+, NO+, MeN+ and MeO+) and also cluster ions Me x O y + (x ≥ 2, 0 ≤y ≤ 2) were detected. Signals of a more molecular type with respect to the reactant gas, e.g. MeNO+, were only found for Co, Ni, Cu, Pd and Pt. From this, one may infer that for the other targets the nitrogen oxides will exist preferentially in a dissociatively adsorbed state at the metal surface. Several aspects of secondary ion emission can be explained assuming a different degree of oxidation for the metals under the influence of reactant gas.
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    Performance for PAN-3 chelate fiber for adsorbing and separating trace uranium—determination by ICP-OES (1990)
    Springer
    Microchimica acta 100 (1990), S. 101-105 
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    ISSN: 1436-5073
    Keywords: PAN-3 chelate fiber ; adsorption ; separation ; uranium ; ICP-OES
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An ICP-OES method is established for polyacrylamidoxime-carboxylic acid chelate fiber (PAN-3) adsorbing and separating trace uranium in waste water. The conditions for quantitative enrichment and desorption uranyl ions are investigated. The stability and the reuse performance of the chelate fiber are discussed. The interference of co-existent ions on uranyl ions as well as the analyses of samples are performed with satisfactory results. The lowest concentration of uranium determined by ICP-OES is 5 μg/l, its RSD is 2.6%.
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    Gravimetric monitoring of adsorption behavior of tetrakis(methylpyrdiniumyl)porphyrin onto quartz crystal surface using an electrode-separated piezoelectric sensor (1998)
    Springer
    Microchimica acta 128 (1998), S. 229-233 
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    ISSN: 1436-5073
    Keywords: porphyrin ; adsorption ; quartz ; piezoelectric ; sensor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The adsorption behavior of 5,10,15,20-tetrakis (4-N-methylpyridiniumyl)-porphyrin (H2TMPyP) from aqueous solutions onto a quartz crystal interface was investigated in situ using an electrode-separated piezoelectric sensor (ESPS). With H2TMPyP adsorbed onto quartz crystal surface of the ESPS, its oscillating frequency decreases linearly with increasing adsorption amount. The adsorption densities obtained in the ESPS method were greater than those determined in a solution depletion method. The influence of surface roughness of quartz crystal and bulk solution properties on the measurement of adsorption density in the ESPS method was discussed.
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    Determination of population pharmacokinetic parameters for amikacin in neonates using mixed-effect models (1998)
    Springer
    European journal of clinical pharmacology 53 (1998), S. 337-341 
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    ISSN: 1432-1041
    Keywords: Key words Amikacin ; Neonate ; Pharmacokinetics ; NONMEM
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: The population pharmacokinetics of amikacin, in neonates, was investigated using the nonlinear mixed effects model (NONMEM). Methods: One hundred and six steady-state amikacin serum levels were obtained from 53 black neonates with a mean gestational age of 35.1 weeks and mean age at the start of treatment of 3.1 days. A one-compartment model was used to fit the data. Results: The final models for clearance (CL) and volume of distribution (V) were: where WT = birth weight (kg) and P = 1.28 for girls and 1.0 for boys. Inclusion of other fixed effect parameters in the model did not significantly improve the fit of the data. The inter-individual variability for CL and V were 18% and 13%, respectively. Intra-individual variability was 29%. Mean (95% CI) values of CL, V and half-life were 0.048 (0.045, 0.051) l· h−1· kg−1, 0.434 (0.414, 0.453) l· kg−1 and 6.4 (6.2, 6.6) h respectively. Conclusion: Birth weight was an important determinant of both CL and V and, in this data set, gender was also found to influence CL. Mean population pharmacokinetic values were within the range of those previously derived for other neonatal populations using traditional methods.
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    Sibutramine pharmacokinetics in young and elderly healthy subjects (1999)
    Springer
    European journal of clinical pharmacology 54 (1999), S. 847-849 
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    ISSN: 1432-1041
    Keywords: Key words Sibutramine ; Pharmacokinetics ; Age
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: To investigate the pharmacokinetics of the pharmacologically active metabolites of sibutramine (metabolites 1 and 2) in healthy young and elderly volunteers following a single oral dose of sibutramine. Methods: This was an open, parallel-group study completed by 12 young (six male, six female; mean age 24.0 years) and 12 elderly (six male, six female; mean age 70.3 years) healthy volunteers. Blood samples were taken at intervals up to 48 h post-dose. Plasma concentrations of metabolites were determined using HPLC-MS. Model-independent pharmacokinetic parameters of the two metabolites were compared for the two age groups. Results: The similarity of the plasma profiles of the two desmethyl metabolites showed that despite the possibility of reduced hepatic function due to age, the rate and extent of formation of these was the same in both young and elderly, i.e. sibutramine metabolism was not impaired in elderly subjects. There were also no significant differences in elimination of metabolite 2 between groups, although the elderly group showed a slight trend for a reduction in kel. Conclusions: The pharmacokinetics of the two pharmacologically active metabolites of sibutramine (metabolites 1 and 2) were not significantly different between the young and elderly groups in this study. Based on this information, a similar dosing regimen would be appropriate for both the young and elderly.
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    Pharmacokinetic and bioequivalence evaluation of two generic formulations of oral artesunate (1998)
    Springer
    European journal of clinical pharmacology 53 (1998), S. 375-376 
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    ISSN: 1432-1041
    Keywords: Key words Artesunate ; Dihydroartemisinin ; Pharmacokinetics ; Bioequivalence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
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    URL: http://dx.doi.org/10.1007/s002280050397
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    Irbesartan does not affect the steady-state pharmacodynamics and pharmacokinetics of warfarin (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 593-598 
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    ISSN: 1432-1041
    Keywords: Key words Irbesartan ; Warfarin ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objectives: To determine whether the initiation or titration of irbesartan alters the pharmacodynamics and/or pharmacokinetics of warfarin in a clinically significant manner, thereby requiring additional monitoring of the anticoagulant effect of warfarin. Methods: Daily doses of warfarin were administered to 16 healthy males for 21 days (10 mg on day 1 and 2.5–10 mg on days 2–21). Irbesartan (300 mg/day) or placebo was concomitantly administered on days 15–21. The pharmacodynamic parameters prothrombin time (PT) and prothrombin time ratio (PTR) were evaluated throughout the study. Plasma and urine samples were collected before and up to 24 h after administration on days 14, 15 and 21 for the determination of the maximum concentration (Cmax), time to reach Cmax (tmax), the area under the concentration–time curve (AUC) of S-warfarin and the cumulative urinary excretion of warfarin and its metabolites. Pre-dose plasma samples were also collected to determine the Cmin of S-warfarin (days 12, 13, 14 and 21) and irbesartan (days 19, 20 and 21). Results: Analysis of PTR data revealed no significant difference between the group mean PTR values at day 22 and those at day 15 (P=0.699). S-warfarin concentrations in plasma and urine, as well as the urinary concentrations of the metabolites of warfarin, were not affected by concomitant single- or multiple-dose administration of irbesartan. Plasma Cmin concentrations of S-warfarin and irbesartan were also not affected. Conclusions: No clinically important effect of irbesartan on the pharmacodynamics and pharmacokinetics of warfarin are likely to occur during concomitant administration; therefore, neither a dosage adjustment of irbesartan or warfarin nor any additional monitoring of the anticoagulant effect of warfarin is necessary.
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    Effect of orlistat on blood cyclosporin concentration in an obese heart transplant patient (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 667-669 
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    ISSN: 1432-1041
    Keywords: Key words Cyclosporin ; Orlistat ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: We detected markedly decreased cyclosporin blood levels in a heart-transplanted patient after the gastrointestinal lipase inhibitor orlistat was accidentally added to the treatment program to control for his obesity. Therefore, we determined cyclosporin plasma concentration time kinetics with and without orlistat reexposition in this patient. Methods: Plasma concentration time kinetics of whole blood cyclosporin levels in an obese heart-transplant patient were measured using a standard monoclonal fluorescence polarisation immunoassay. Results were obtained in hourly intervals up to 12 h without and with co-therapy of 3 × 120 mg orlistat (Xenical, Roche Ltd., Switzerland). The orlistat re-exposition was started the day before taking blood samples. Results: Cyclosporin trough levels (98 ng/ml vs 52 ng/ml), maximum concentrations (532 ng/ml vs 74 ng/ml) and the area under the blood drug concentration-time curve (2832 ng h ml−1 vs 700 ng h ml−1) were greatly reduced with orlistat. Conclusions: Orlistat markedly decreased blood cyclosporin concentrations, possibly due to an interference with its absorption in the small intestine. To avoid potential dangerous under-immunosuppression, orlistat should not be used in patients taking cyclosporin.
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    Pharmacokinetics and pharmacodynamics of candesartan cilexetil in patients with normal to severely impaired renal function (1999)
    Springer
    European journal of clinical pharmacology 54 (1999), S. 953-958 
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    ISSN: 1432-1041
    Keywords: Key words AT1 receptor antagonist ; Blood pressure ; Candesartan cilexetil ; Candesartan ; Pharmacokinetics ; Renin angiotensin system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: We studied the pharmacokinetics and pharmacodynamics of single and multiple doses of candesartan cilexetil 8 mg per day in hypertensive patients with different degrees of renal function impairment. Candesartan is an angiotensin II subtype 1 (AT1) receptor antagonist that is administered orally as candesartan cilexetil which is converted in the active compound. Methods: Twenty-three patients were included, divided into groups according to creatinine clearance (cr cl. group A 〉60 nl · min−1 · 1.73 m−2, group B 30–60 ml · min−1 · 1.73 m−2 and group C 15–30 ml · min−1 · 1.73 m−2). Results: Trough serum concentrations of candesartan were higher in group C compared with group A. The values did not increase after multiple dosing, indicating absence of accumulation. There was a significant negative correlation between the area under the concentration-time curve extrapolated to time infinity (AUCinf) and the glomerular filtration rate (GFR) indicating a lower renal clearance of candesartan in patients with impaired renal function. The onset of haemodynamic and hormonal effects was gradual. During the single-dose study blood pressure as well as plasma renin activity (PRA) and angiotensin II were unchanged at peak. At day 5 of the multiple-dose study blood pressure was lower and both PRA and angiotensin II were higher compared with baseline. Conclusion: Although serum trough levels increased during repeated administration and half-life was higher in patients with impaired renal function, candesartan cilexetil at a dose of 8 mg per day does not lead to drug accumulation in these patients. This dose is effective in lowering blood pressure and appears to be suitable for patients with renal function impairment.
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    Pharmacokinetics of a novel 5-lipoxygenase inhibitor (ABT-761) in pediatric patients with asthma (1998)
    Springer
    European journal of clinical pharmacology 54 (1998), S. 715-719 
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    ISSN: 1432-1041
    Keywords: Key words ABT-761 ; Pharmacokinetics ; Asthma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: The pharmacokinetics of an N-hydroxyurea analog, ABT-761 in asthmatic pediatric patients with asthma were investigated. Methods: A total of 24 patients were enrolled into this 8-day single- and multiple-dose study. Patients received daily doses of ABT-761 according to their body weight: patients of 20–38 kg received 50 mg; patients 〉38 kg but ≤55 kg received 100 mg, and patients ≥55 kg received 150 mg. Results: The mean values for the terminal phase t1/2 were 16–17 h after multiple-dose administration. When normalized for body weight, the mean day 8 Clf values for 50-, 100-mg, and 150-mg doses were 0.57 (n = 13), 0.51 (n = 10), and 0.43 (n = 1) ml · min−1 · kg−1, respectively, while the mean Vz/f values ranged from 0.75 to 0.77 l · kg−1. The mean accumulation ratio observed (day 8 to day 1 AUC0–24 ratio) of ABT-761 was approximately 1.7, which is consistent with the t1/2 of this drug. Body weight, age, and body surface area were virtually identical in explaining the variability in dose-normalized Cmax and AUC values (R 2 = 0.61–0.68). The percents of variance explained by these three variables were within a range of 3% for each pharmacokinetic parameter. Conclusions: The pharmacokinetics of ABT-761 in children were similar to those previously reported in adults. Body weight, age, or body surface area can be used to provide dosing adjustment for ABT-761 in pediatric patients.
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    Can oral contraceptive steroids influence the elimination of nifedipine and its primary pryidine metabolite in humans? (1998)
    Springer
    European journal of clinical pharmacology 54 (1998), S. 729-734 
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    ISSN: 1432-1041
    Keywords: Key words Oral contraceptives ; Nifedipine ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: To investigate the influence of oral contraceptives on cytochrome P450 3A4 (P450NF) activity. Methods: In 23 healthy women, the pharmacokinetics of nifedipine and its main metabolite dehydronifedipine in plasma were assessed after a single oral dose, prior to and after intake of one of two oral contraceptive formulations, one containing 2 mg dienogest and 0.03 mg ethinylestradiol (group A) and the other containing 0.125 mg levonorgestrel and 0.03 mg ethinylestradiol (group B). Results: While the intake of two oral contraceptives for 21 days did not influence the plasma concentration-time curve of unchanged nifedipine, mean AUC0–23.5 h and the mean Cmax values of dehydronifedipine were significantly lower in both groups tested/(24% in group A and 25% in group B). This observation may indicate a reduced formation rate of metabolites and reflects an inhibition of cytochrome P450 3A4 activity. The activation of the same or other metabolic degradation mechanism(s) could explain this result. Conclusion: The investigation presented demonstrates the importance of metabolite measurement when in vivo studies are undertaken to investigate different influences on drug metabolizing ability.
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    Pharmacokinetics and safety of propiverine in patients with fatty liver disease (1998)
    Springer
    European journal of clinical pharmacology 54 (1998), S. 767-771 
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    ISSN: 1432-1041
    Keywords: Key words Propiverine ; Fatty liver disease ; Pharmacokinetics ; Adverse effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: The present study was designed to assess the pharmacokinetics of propiverine after single and multiple dosing in patients with and without fatty liver disease. Methods: The serum concentration-time curves of propiverine and its main metabolite propiverine-N-oxide were investigated in 12 patients with mild to moderate impairment of liver function (mean antipyrine clearance 26.0 ml · min−1) and in 12 controls (antipyrine clearance 42.8 ml · min−1). Subjects were treated orally with propiverine hydrochloride (Mictonorm) for 5 days (15 mg t. i. d.) to reach steady state. Results: No significant differences were observed for propiverine and its main metabolite with regard to peak serum concentration (Cmax), area under the serum concentration-time curve (AUC) and elimination half-life (t1/2). Adverse events were reported by 12 patients. Five patients with fatty liver disease and seven patients with normal liver function complained of dry mouth and/or blurred vision. All adverse events reported were transient and mild. Conclusion: No pharmacokinetic differences relevant for safety were observed, comparing patients with and without fatty liver disease following repeated oral administration of propiverine. Thus there seems to be no need to adjust the dose in patients with mild to moderate impairment of liver function.
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    Limited-sampling strategy models for estimating the area under the plasma concentration–time curve for amlodipine (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 651-657 
    Details
    ISSN: 1432-1041
    Keywords: Key words Amlodipine ; Limited-sampling models ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: Develop and validate limited-sampling strategy (LSS) models for estimating the area under the plasma concentration versus time curve (AUC) of amlodipine, using data from a bioequivalence study. Methods: Sixteen healthy volunteers received single 5-mg oral doses of amlodipine, as reference or test formulation, at a 14-day interval, in a randomized, crossover protocol. Plasma concentrations of amlodipine (n = 288), measured by mass spectrometry, were used to develop LSS models. Results: Linear regression analysis of the AUC0–72 and a “jack-knife” validation procedure revealed that LSS models based on two sampling times (12 h and 48 h) predict accurately (R2 = 0.99; bias〈0.01%; precision = 0.03%) the AUC0–72 of amlodipine for each formulation. Validation tests indicate that the 2-point LSS model developed for the reference formulation predicts accurately (R2〉0.90): (a) the individual AUC0–72 for the test formulation in the same group of volunteers; (b) the individual AUC0–72 for the same reference formulation in another bioequivalence study in Brazilian volunteers; (c) the average AUC0–72 reported in seven additional international studies performed under protocols similar to the present investigation; (d) the individual AUC0–72 corresponding to concentration data points provided by a first-order compartmental pharmacokinetic model, when the relative values of either the absorption rate (K abs) or the bioavailability (F) model parameters were set at 0.85 or 0.6, of their respective original values. Conclusions: The 2-point LSS models developed in the current study predict accurately the AUC of amlodipine under a variety of experimental conditions and, thus, may be valuable for exploring the relationships between the pharmacokinetics and pharmacodynamics of this calcium antagonist, at reduced costs of sample acquisition and analysis, and avoiding sampling at “unsociable” hours.
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    Bioavailability of intranasal formulations of dihydroergotamine (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 677-680 
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    ISSN: 1432-1041
    Keywords: Key words Dihydroergotamine ; Absorption ; Intranasal ; Randomly methylated β-cyclodextrin (RAMEB) ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: A comparison of the pharmacokinetic properties of two novel intranasal preparations of dihydroergotamine mesilate (DHEM) with a commercially available intranasal preparation. Methods: Two intranasal formulations of DHEM in combination with randomly methylated β-cyclodextrin (RAMEB) were prepared. Subsequently, in an open, randomised, crossover study in nine healthy volunteers, the following medication was administered: 2 mg DHEM/2% RAMEB nasal spray ( =two puffs of 100 μl); 2 mg DHEM/4 mg RAMEB nasal powder; 2 mg Diergo nasal spray ( =four puffs of 125 μl); 0.5 mg DHEM i.m., and 2 mg DHEM solution p.o. Results: No statistically significant differences were found in maximum plasma concentration (Cmax), time to reach Cmax (tmax), area under plasma concentration–time curve (AUC0–8 h), Frel(t=8 h) and Cmax/ AUC(t=8 h) for the three intranasal preparations. The relative bioavailabilities of the DHEM/RAMEB nasal spray, the DHEM/RAMEB nasal powder and the commercially available DHEM nasal spray were 25%, 19% and 21%, respectively, in comparison with i.m. administration. The relative bioavailability after oral administration was 8%. Conclusion: The pharmacokinetic properties of the novel intranasal preparations are not significantly different from the commercially available nasal spray. Advantages of the DHEM/RAMEB nasal spray are (1) less complicated handling, (2) reduction of the number of puffs and (3) a preference by the volunteers.
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    Influence of the cytochrome P4502D6*4 allele on the pharmacokinetics of controlled-release metoprolol (1998)
    Springer
    European journal of clinical pharmacology 54 (1998), S. 469-474 
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    ISSN: 1432-1041
    Keywords: Key words CYP2D6 ; Genetic polymorphism ; Metoprolol ; Pharmacokinetics ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Aim: The aim of the present paper was to compare the pharmacokinetics of metoprolol in homozygous Caucasian volunteers for the wild-type CYP2D6 allele (CYP2D6*1/CYP2D6*1) and heterozygous (CYP2D6*1/CYP2D6*4) Caucasians. Methods: Thirty-six unrelated healthy male Caucasians were screened for two of the most frequently occurring mutant alleles (CYP2D6*3 and CYP2D6*4) using polymerase chain reaction (PCR). Twenty-four volunteers with a genotype suggesting a rapid hydroxylator phenotype were enrolled in a bioequivalence trial and each received in a randomized, cross-over fashion one of the three formulations compared. Each formulation contained 200 mg metoprolol tartrate/(tablet). In each of the three periods of the trial, one of the formulations was administered under fasting conditions in the morning on 4 consecutive days. Blood for quantification of metoprolol was drawn immediately before the last dose and in selected time intervals thereafter. A sensitive and specific high-performance liquid chromatography (HPLC) method with fluorescence detection was applied for the quantification of metoprolol. Pharmacokinetic parameters were determined for each subject and statistically compared in two groups of 16 homozygous (CYP2D6*1/CYP2D6*1) and six heterozygous (CYP2D6*1/CYP2D6*4) volunteers. Results: Significant differences between homozygous and heterozygous individuals were observed for all pharmacokinetic parameters. The AUC in the course of one those interval of 24 h (AUCτ), minium steady-state concentration (Cmin ss) and average steady-state concentration (Cav ss) values for heterozygous individuals were more than twice those of individuals. Significantly higher values for Css max , t1/2, half-value duration (HVD) and mean residence time (MRT) were also observed in heterozygous volunteers. The higher concentrations of metoprolol in heterozygous individuals also had pharmacodynamic consequences, namely, greater heart rate and blood pressure reduction.
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    Distribution and metabolism of N G-nitro-l-arginine methyl ester in patients with septic shock (1998)
    Springer
    European journal of clinical pharmacology 54 (1998), S. 627-631 
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    ISSN: 1432-1041
    Keywords: Key wordsl-NAME ; Pharmacokinetics ; Septic shock
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: The pharmacokinetics of N G-nitro-l-arginine methyl ester (l-NAME), an inhibitor of nitric oxide (NO) synthesis, was investigated in patients with septic shock. Methods: Blood was sampled at intervals before, during and after 12-h infusion of l-NAME 1 mg · kg−1 · h−1 in nine septic shock patients for determination of plasma concentrations by high-performance liquid chromatography (HPLC). In three patients the renal clearance of the drug was determined. Results: Incubation of l-NAME with plasma and blood in vitro revealed hydrolysis to N G-nitro-l-arginine (l-NOARG), the active inhibitor of NO synthesis. l-NOARG did not undergo further degradation. Continuous intravenous infusion of 1 mg · kg−1 · h−1 of l-NAME for 12 h in patients with septic shock increased blood pressure and resulted in increasing plasma concentrations of l-NOARG (Cmax 6.2 μg · ml−1 at 12 h) whereas l-NAME concentrations reached a plateau within 1.5 h (Cmax 1.0 μg · ml−1). After the infusion was stopped l-NAME disappeared from the plasma rapidly (half-life 19.2 min) whereas l-NOARG concentration declined slowly (half-life 22.9 h). The calculated volume of distribution for l-NAME was 0.45 l · kg−1 body weight and 1.96 l · kg−1 for l-NOARG. The renal clearance for l-NOARG was 3.5% of total body clearance for l-NOARG, whereas l-NAME could not be detected in urine. Conclusion: We conclude that vasoconstriction with l-NAME in septic patients may result from hydrolysis to l-NOARG, the active inhibitor of NO synthesis. The long plasma half-life and large volume of distribution for l-NOARG suggests extensive distribution to extravascular tissues. Since renal excretion is minimal, elimination of the metabolite l-NOARG follows other pathways.
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    Estimation of the area under the concentration-versus-time curve of carboplatin following irinotecan using a limited sampling model (1998)
    Springer
    European journal of clinical pharmacology 54 (1998), S. 725-727 
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    ISSN: 1432-1041
    Keywords: Key words Carboplatin ; Irinotecan ; Limited sampling model ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objectives: The aim of this study was to develop limited sampling models for estimating the area under the concentration-versus-time curve (AUC) of carboplatin. Methods: Based on pharmacokinetic analyses of 14 patients who received 300 mg · m2 of carboplatin over a 90-min infusion following irinotecan, we developed limited sampling models with stepwise multiple linear regression analysis. We validated these models to be unbiased and precise using pharmacokinetic data of a second group of 14 patients. We also compared the observed and the predicted AUC in the patients using Calvert's formula with the patients' renal function. Results: We developed the following models: AUC (mg · ml−1 · min) = 0.784 × C4 + 1.30 (r 2 = 0.930) and AUC = 0.100 × C0.25 + 0.597 × C4 + 0.140 (r 2 = 0.992), where C0.25 and C4 denote unbound plasma concentrations (μg · ml−1) of carboplatin at 0.25 h and 4 h after the end of infusion, respectively. These models were validated to be unbiased and precise: a mean prediction error (MPE) with standard deviation (SD) = 2.41 (9.45)% and a root mean squared error (RMSE) = 9.42% for the one-sample model, and MPE with (SD) = 1.22 (5.56)% and RMSE = 5.49% for the two-sample model. We also calculated predicted AUC in the patients using Calvert's formula: MPE with (SD) =−5.87 (21.5)% and RMSE = 21.5%. Conclusions: These estimations were, as expected, more accurate than the prediction using Calvert's formula based on patients' renal function. The result of this study confirmed the idea that the pharmacokinetic parameters derived from limited sampling models would be more suitable for pharmacokinetic analysis of carboplatin than those obtained using Calvert's formula.
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    Pharmacokinetics of oxypolygelatine in healthy volunteers (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 49-51 
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    ISSN: 1432-1041
    Keywords: Key words Oxypolygelatine ; Pharmacokinetics ; Healthy volunteers ; Tolerability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective/methods: The pharmacokinetics of the plasma substitute oxypolygelatine (OPG) were studied in 12 healthy volunteers after single-dose administration of 27 ml · kg−1 body weight, with a maximum of 2000 ml. OPG was determined in plasma and urine over 48 h after the infusion. Peak plasma OPG concentrations at the end of the infusion were determined to 4.600 (623) μg · ml−1, the area under the plasma concentration/time curve (AUC0∞) was calculated to 70.135 (15.861) μg · h · ml−1. Results: The model-independently calculated volume of distribution came to 23.1 (4.8) l with a clearance total is (Cltot) of 24.6 (6.8) ml · min−1. The initial half-life according to a three-compartment model came to 0.3 (0.2) h, followed by a distribution half-life of 3.1 (2.6) h and a terminal elimination half-life of 13.4 (2.2) h. Cumulative urinary excretion of OPG was 64% after 48 h. Conclusion: This low recovery rate may be explained by the distribution of OPG into the extravascular space and subsequent degradation in tissue sites.
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    Absence of interaction between erythromycin and a single dose of clozapine (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 221-226 
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    ISSN: 1432-1041
    Keywords: Key words Clozapine ; Erythromycin ; CYP3A4 ; Pharmacokinetics ; Drug interaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: To study the suggested pharmacokinetic interaction between erythromycin, a strong inhibitor of CYP3A4, and clozapine. Methods: Twelve healthy male volunteers received a single dose of 12.5 mg of clozapine alone or in combination with a daily dose of 1500 mg erythromycin in a randomised crossover study. Clozapine and its metabolites clozapine-N-oxide and desmethyl-clozapine were measured in serum samples which were collected during a 48 h period and in a sample of the urine secreted over the interval 0–12 h. Results: There were no significant differences in mean area under the serum concentration time curves (1348 (633) nmol h · 1−1 in the control phase and 1180 (659) nmol h · 1−1 in the erythromycin phase), terminal half-lives (19 (13) h and 15 (6) h, respectively), peak serum concentrations (92 (53) nmol · 1−1 and 77 (40) nmol · 1−1, respectively), time to peak serum concentrations (1.4 (0.7) h and 1.5 (1.0) h, respectively) or apparent oral clearances of clozapine (34 (15) l · h−1 and 46 (37) l · h−1, respectively). There were no significant differences in partial metabolic clearances to clozapine-N-oxide (5.1 (3.6) l · h−1 and 7.8 (9.4) l · h−1, respectively) or to desmethyl-clozapine (1.5 (1.3) l · h−1 and 1.8 (1.7) l · h−1, respectively) or in renal clearances of clozapine (0.8 (0.5) l · h−1 and 1.0 (0.7) l · h−1, respectively) between the two phases. Conclusion: These results demonstrate that erythromycin at a clinically relevant dosage does not inhibit the metabolism of clozapine. Hence, CYP3A4 seems to be of minor importance in the disposition of clozapine in humans at least when clozapine is taken at a low single dose.
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    Lack of influence of menstrual cycle and premenstrual syndrome diagnosis on pregnanolone pharmacokinetics (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 125-130 
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    ISSN: 1432-1041
    Keywords: Key words Pregnanolone ; Pharmacokinetics ; Premenstrual syndrome
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: Pregnanolone is a 3α-hydroxylated-5β-reduced metabolite of the female sex steroid hormone progesterone. The compound is currently being evaluated for anaesthetic purposes. Previous studies have indicated a differential physiological response across the menstrual cycle and a different response in patients with premenstrual syndrome (PMS). This study was undertaken to determine whether hormonal changes during the menstrual cycle influence pregnanolone pharmacokinetics and to compare PMS diagnosis-related differences in pregnanolone pharmacokinetics. Methods: Seven patients with premenstrual syndrome and seven female controls were given three increasing doses of pregnanolone in the follicular and luteal phase of the menstrual cycle. Results: Mean pregnanolone elimination half-life varied between 28.4 min and 31.8 min and clearance between 59.6 ml · min−1 · kg−1 and 64.0 ml · min−1 · kg−1, depending on diagnostic group and cycle phase. No significant differences in pregnanolone pharmacokinetic properties were found between PMS patients and controls in either phase of the menstrual cycle. Furthermore, no differences in pharmacokinetic variables were detected between cycle phases. Conclusion: Pregnanolone pharmacokinetics do not differ between follicular and luteal phase of the menstrual cycle, nor between PMS patients and control subjects.
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    URL: http://dx.doi.org/10.1007/s002280050606
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    Development of a general method of limited sampling for the determination of AUC for a drug that displays two-compartment pharmacokinetics (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 213-219 
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    ISSN: 1432-1041
    Keywords: Key words Limited sampling ; Area under the curve ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objectives: To develop a method of limited sampling that would enable accurate estimation of the area under the concentration time curve (AUC) when using the log trapezoidal method. Methods: A series of datasets were simulated. Each dataset comprised 1000 subjects. Each subject was “administered” an intravenous bolus dose of a drug that displays two compartment pharmacokinetics. In the first series of simulations, a variety of combinations of the number of sampling times (K) and number of replicate measurements (R) at each of these times were tested, where K × R = 12 (i.e. N = 12). The times that each of the K samples were taken were chosen to be those that divided the AUC into K − 1 trapezoids of equal area. The concentration-time curves were estimated based on a priori estimates of the population parameters. The best combination of K and R was tested under various conditions of parameter variability and assay variability. The combinations were compared with a conventional sampling strategy, where N = 12, K = 12 (R = 1). Results: The combination K = 4 and R = 3 proved to be the “best”. It had similar accuracy to the conventional method. The best limited sampling combination was superior to the conventional method when assay variability was high (CV = 30%), was similar when assay variability was 15%, but the conventional method became statistically superior when assay variability was 7.5% or less. The accuracy of the best limited sampling combination was inversely related to the parameter variability. If K was set to 4 and R allowed to increase to 6 (i.e. N≠ 12), there was no further gain in accuracy. Conclusion: The proposed method of limited sampling is at least as accurate as the conventional intensive sampling technique, but more efficient in terms of sampling.
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    Renal handling of drugs in the healthy elderly Creatinine clearance underestimates renal function and pharmacokinetics remain virtually unchanged (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 205-211 
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    ISSN: 1432-1041
    Keywords: Key words Elderly ; Pharmacokinetics ; Renal function
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: It is commonly assumed that renal function, and in parallel the excretion of drugs, is considerably reduced in the elderly. Endogenous creatinine clearance or indirect estimates of this parameter are generally recommended for adapting drug dosage. The present study evaluates the validity of both assumptions. Methods: We compared pharmacokinetics (and pharmacodynamics) of 50 mg atenolol, 800 mg piracetam and 25 mg hydrochlorothiazide plus 50 mg triamterene in ten healthy young [25 (2) years] and 11 healthy elderly subjects [68 (5) years]. Inulin (Cin) and para-aminohippurate [PAH (CPAH)] clearance (infusion clearance technique), endogenous (CCr) and calculated (Cockroft-Gault) creatinine clearance, analysis of drugs and their metabolites (HPLC), were performed. Renal haemodynamics and the pharmacokinetics of β-adrenergic blocking agent, diuretics and the nootropic agent piracetam, respectively, were measured on separate days. Results: Cin was significantly (P 〈 0.01) lower in the healthy elderly subjects [104 (12) vs 120 (14) ml · min−2 · 1.73 m−2 in the young], but remained within the normal range (〉90 ml · min−2 · 1.73 m−2). In contrast, CCr was even lower in healthy elderly subjects [95 (24) vs 121 (20) ml · min−1 in the young], and the Cockroft-Gault clearance underestimated true glomerular filtration rate (GFR) even more seriously [74 (17) vs 122 (16) ml · min−1]. For atenolol the mean area under the curve (AUC) was similar in both groups [3.16 (0.48) μg · h−1 · ml−1 in the elderly vs 3.01 (0.30) in the young], as was the mean maximal plasma concentration [0.42 (0.07) vs 0.44 (0.06) μg · ml−1], but the proportion of the drug excreted in urine was marginally (P 〈 0.025) lower in the elderly. Similar results were obtained for hydrochlorothiazide, whereas no marked differences between the groups were found for triamterene and its metabolite. Furthermore, the pharmacodynamic action of diuretics was not significantly altered in the elderly. Conclusions: The true GFR of the healthy elderly remains within the normal range and is underestimated by creatinine clearance and more so by its surrogate (Cockroft-Gault clearance). In parallel, pharmacokinetics of renally excreted drugs are not affected in the healthy elderly to a clinically significant extent. For drugs with a narrow therapeutic window, indirect estimates of GFR appear to be an unreliable means for calculating correct dosage in the elderly.
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    The effect of grapefruit juice on the pharmacokinetics of orally administered verapamil (1998)
    Springer
    European journal of clinical pharmacology 54 (1998), S. 337-340 
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    ISSN: 1432-1041
    Keywords: Keywords Verapamil ; Grapefruit juice ; Pharmacokinetics ; Hypertension
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: To investigate the effect of grapefruit juice (GJ) on the pharmacokinetics of orally administered verapamil in hypertensive patients. Methods: Ten hypertensive patients on chronic verapamil treatment participated in a two-day study. On day 1 200 ml of water was given 1 hour before, and together with the morning verapamil dose; on the day 2, water was replaced by GJ in the same order. Serial blood samples were collected and the concentrations of verapamil and its main dealkylated metabolite (D-617) were determined by high-performance liquid chromatography (HPLC). The area under the concentration versus time curve of verapamil (AUCv) and its metabolite D-617 (AUCM) were calculated before and after GJ ingestion. The peak serum concentration (Cmax) and the time until its appearance (tmax) were also determined. Results: GJ did not affect Cmax, tmax, AUCv or AUVm. The AUCv/AUCm ratio (AUCR) was slightly, but significantly, increased after GJ (1.67 vs 1.92). Conclusions: A single administration of GJ with short-acting verapamil has no significant effect on the pharmacokinetics, of verapamil.
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    Comparative pharmacokinetic study of oral and rectal formulations of artesunic acid in healthy volunteers (1998)
    Springer
    European journal of clinical pharmacology 54 (1998), S. 411-414 
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    ISSN: 1432-1041
    Keywords: Key words Artesunic acid ; Pharmacokinetics ; Malaria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: A single cross-over, comparative pharmacokinetic study of oral and rectal formulations of 200 mg artesunic acid in 12 healthy Malaysian volunteers is reported. Methods: Plasma concentrations of artesunic acid and dihydroartemisinin were determined simultaneously by HPLC with electrochemical detection. The test drug was well tolerated and no undesirable adverse effects were observed. Results: Comparison of pharmacokinetic parameters of artesunic acid after oral and rectal administration showed statistically significant differences in t max and AUC, with no changes for C max and t 1/2. As for dihydroartemisinin, differences were observed for t max and C max but not for AUC. Conclusion: There appear to be pharmacokinetic differences between oral and rectal modes of administration. The significance of these findings should be explored in malaria patients before appropriate therapeutic regimens are devised.
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    Population pharmacokinetic analysis of pirmenol in healthy volunteers and patients with arrhythmia (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 77-78 
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    ISSN: 1432-1041
    Keywords: Key words Pirmenol ; Arrhythmia ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
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    URL: http://dx.doi.org/10.1007/s002280050596
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    Grapefruit juice has no effect on quinine pharmacokinetics (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 393-398 
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    ISSN: 1432-1041
    Keywords: Key words Grapefruit juice ; Quinine ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: As quinine is mainly metabolised by human liver CYP3A4 and grapefruit juice inhibits CYP3A4, the effect of grapefruit juice on the pharmacokinetics of quinine following a single oral dose of 600 mg quinine sulphate was investigated. Methods: The study was carried out in ten healthy volunteers using a randomised cross-over design. Subjects were studied on three occasions, with a washout period of 2 weeks. During each period, subjects received a pretreatment of 200 ml orange juice (control), full-strength grapefruit juice or half-strength grapefruit juice twice daily for 5 days. On day 6, the subjects were given a single oral dose of 600 mg quinine sulphate with 200 ml of one of the juices. Plasma and urine samples for measurement of quinine and its major metabolite, 3-hydroxyquinine, were collected over a 48-h period and analysed by means of a high-performance liquid chromatography method. Results: The intake of grapefruit juice did not significantly alter the oral pharmacokinetics of quinine. There were no significant differences among the three treatment periods with regard to pharmacokinetic parameters of quinine, including the peak plasma drug concentration (Cmax), the time to reach Cmax (tmax), the terminal elimination half-life (t1/2), the area under the concentration–time curve and the apparent oral clearance. The pharmacokinetics of the 3-hydroxyquinine metabolite were slightly changed when volunteers received grapefruit juice. The mean Cmax of the metabolite (0.25 ± 0.09 mg l−1, mean ± SD) while subjects received full-strength grapefruit juice was significantly less than during the control period (0.31 ± 0.06 mg l−1, P 〈 0.05) and during the intake of half-strength grapefruit juice (0.31 ± 0.07 mg l−1, P 〈 0.05). Conclusion: These results suggest that there is no significant interaction between the parent compound quinine and grapefruit juice, so it is not necessary to advise patients against ingesting grapefruit juice at the same time that they take quinine. Since quinine is a low clearance drug with a relatively high oral bioavailability, and is primarily metabolised by human liver CYP3A4, the lack of effect of grapefruit juice on quinine pharmacokinetics supports the view that the site of CYP inhibition by grapefruit juice is mainly in the gut.
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    Pharmacokinetics of oral entacapone after frequent multiple dosing and effects on levodopa disposition (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 461-467 
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    ISSN: 1432-1041
    Keywords: Key words Entacapone ; Levodopa ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: Entacapone is a peripherally acting catechol O-methyltransferase (COMT) inhibitor used as an adjunct to each daily levodopa/dopa decarboxylase (DDC) inhibitor dose in the treatment of Parkinson's disease. Parkinsonian patients with advanced disease and motor fluctuations take several doses of levodopa daily, due to the short action of levodopa in this patient population. The present study was conducted in order to evaluate the pharmacokinetics of entacapone after multiple dosing and the pattern of COMT inhibition in erythrocytes during the first day of dosing as well as during steady state. Furthermore, the disposition of plasma levodopa and carbidopa was studied after a single dose of levodopa/carbidopa during the same conditions. Methods: Twelve healthy male volunteers received 200 mg entacapone eight times daily during study day 1 and day 6 at 2-h intervals from 0800 hours to 2200 hours. During days 3, 4 and 5, 200 mg of entacapone was taken ten times daily, from 0800 hours to 0200 hours on the following day. One levodopa/carbidopa tablet (100/25 mg) was taken on study day 1 and day 6 at 1000 hours. Plasma entacapone concentrations and erythrocyte COMT activities were measured frequently on study days 1–2 and 6–7, and twice daily on study days 3–5. Pharmacokinetic parameters calculated from plasma drug concentrations on days 1–2 and 6–7 were compared with each other. Results: There were no differences in maximal plasma concentration (Cmax), time to maximal drug concentration in plasma (tmax), elimination half-life (t1/2) and area under the plasma concentration–time curve (AUC) of entacapone between day 1 and day 6. The mean t1/2 values of entacapone were 1.3 h and 1.8 h during the first and sixth days, respectively; the difference was not significant. No signs of accumulation of entacapone were noted after the first day. Entacapone reduced erythrocyte COMT activity after the first dose, and this effect was quite stable during frequent dosing. There were no indications of accumulation of COMT inhibition during frequent dosing of entacapone. There were no between-day differences in Cmax, t1/2 (2.4 h on days 1–2 and 2.3 h on days 6–7) or AUC of levodopa, whereas tmax occurred at 0.8 h on day 1 and at 1.2 h on day 6 (P = 0.03). There were no between-day differences in the pharmacokinetic parameters (Cmax, tmax and AUC) of carbidopa. Conclusion: Even when dosed frequently, there are neither indications of accumulation of entacapone nor of its COMT inhibiting activity.
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    The effect of short-term dipyrone administration on cyclosporin pharmacokinetics (1999)
    Springer
    European journal of clinical pharmacology 55 (1999), S. 475-478 
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    ISSN: 1432-1041
    Keywords: Key words Cyclosporin ; Dipyrone ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Background: A large number of drugs have been shown to affect the metabolism of cyclosporin A (CSA) and, since cyclosporin is characterized by a narrow therapeutic range, the consequences of such drug interactions may often be of clinical importance. Objective: To evaluate the effect of short-term administration of dipyrone on steady state CSA pharmacokinetics. Methods: Six kidney- and two heart-transplanted patients on chronic CSA therapy participated in this study, which consisted of two 4-day study periods separated by 3-week washout periods. The patients received, in addition to their usual drugs, dipyrone 500 mg or placebo t.i.d., as identical-looking tablets, and the order of administration was randomized. CSA concentrations were measured in whole blood by means of radio-immunoassay (CYCLO-Trac SP) daily during the study periods and periodically over 24 h on the fourth study day. Results: CSA concentrations over time were reduced after dipyrone (ANOVA, P 〈 0.01), but statistical significance was noted only at 2, 4, 5 and 10 h after drug intake (P 〈 0.05). Peak CSA concentration was not altered by dipyrone, but the time required to reach maximal concentration was longer with dipyrone treatment than with the placebo (3.8 ± 2.6 h vs 2.1 ± 0.6 h, P 〈 0.05). No consistent changes were noted for CSA trough level, elimination half-life and area under the concentration–time curve from 0 h to 12 h. Separate analysis of the kidney transplanted patients yielded similar results. Conclusions: Short-term administration of dipyrone is associated with a mild decrease in CSA blood concentration, which is most prominent in the first few hours after drug intake. In practice, no dose adjustment of CSA seems to be indicated during a short course of dipyrone treatment.
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    Investigation of possible pharmacokinetic and pharmacodynamic interactions between epanolol and digoxin (1990)
    Springer
    European journal of clinical pharmacology 38 (1990), S. 505-507 
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    ISSN: 1432-1041
    Keywords: Digoxin ; epanolol ; plasma concentrations ; STI ; Pharmacokinetics ; healthy male volunteers ; drug interaction ; adverse reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary. The possibility of a pharmacokinetic and/or pharmacodynamic interaction between epanolol and digoxin has been investigated in 10 healthy male subjects taking digoxin 0.375 mg daily for 14 days. During that period epanolol 200 mg daily or matching placebo was also given, each for 7 days, according to a double-blind, randomized cross-over plan. The plasma digoxin concentration-time profiles after 7 days of concomitant placebo or epanolol were comparable. Trough and peak plasma digoxin levels were similar (placebo: 0.84 and 2.62 ng · ml−1; epanolol: 0.87 and 2.46 ng · ml−1). The renal clearances of digoxin and creatinine were lower during treatment with epanolol, but the differences were not significant (placebo 142.0 and 126.5 ml · min−1; epanolol 105.7 and 109.3 ml · min−1). STI indexes were lower during treatment with digoxin plus epanolol, than after digoxin alone. The difference was significant for QS2I (513 versus 503 ms), PEPI (119 versus 112 ms) and PEP/LVET (0.286 versus 0.304). The observations suggest that in healthy volunteers there is no pharmacokinetic interaction between epanolol and digoxin, and that epanolol does not interfere with the positive inotropic action of digoxin.
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    Evolution of atenolol kinetics when hypothyroidism is corrected (1990)
    Springer
    European journal of clinical pharmacology 38 (1990), S. 185-188 
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    ISSN: 1432-1041
    Keywords: Atenolol ; Hypothyroidism ; Drug absorption ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A single oral dose of atenolol 100 mg was given to 7 hypothyroid patients (4 F, 3 M), before and after correction of hypothyroidism, mean delay 3.5 months (2 to 6.5 months). There was no change in the elimination parameters of atenolol, but the maximal plasma atenolol concentration was increased (1.66 to 7.37 mg·l−1) as was the AUC (14.9 to 52.1 mg·l−1·h) when the hypothyroidism had been treated. Only one patient differed: he had had a supra-selective vagotomy, and had similar curves before and after treatment of the hypothyroidism, both being similar to the plasma concentration curves found in the other patients after correction of the hypothyroidism. The results suggest an increase in the bioavailability of atenolol when hypothyroidism is corrected. The findings in the patient with vagotomy suggest that the decreased bioavailability during hypothyroidism might be related to changes in intestinal pH. Further studies are needed of the impact of hypothyroidism on gastric and pancreatic or biliary function and its consequences for drug absorption, and drug pharmacokinetics.
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    Placental transfer and perinatal pharmacokinetics of betaxolol (1990)
    Springer
    European journal of clinical pharmacology 38 (1990), S. 477-483 
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    ISSN: 1432-1041
    Keywords: Betaxolol ; Milk ; Neonates ; Placental Transfer ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Betaxolol levels in blood were monitored in the perinatal period in 28 pregnant hypertensive women and in their babies. In the mothers betaxolol concentrations at delivery ranged from 〈1 to 115 ng · ml−1 after doses of 10 to 40 mg · day−1. The apparent blood half-life was 15.6 to 22.1 h mean (19 h). Umbilical cord levels indicated a rapid equilibrium between fetal and maternal units (ratio 0.93) within few hours after dosing. Milk betaxolol concentrations, measured in few cases, exceeded those in blood by a factor of 3. Amniotic fluid concentrations were similar to those observed in maternal venous blood and umbilical cord blood. In neonates, the blood betaxolol half-life ranged from 14.8 to 38.5 h, with a definite trend towards a negative correlation with gestational age. A 11–61% rise in the betaxolol concentration was observed in 64% of the neonates during the first 12 h of extrauterine life. The data indicate that betaxolol kinetics is not altered in pregnant women and they stress the need for careful and prolonged (72–96 h) intensive monitoring of neonates born to hypertensive mothers treated with β-blocking agents.
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    Pharmacokinetics of aspirin in aged indians (1990)
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    European journal of clinical pharmacology 38 (1990), S. 85-86 
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    ISSN: 1432-1041
    Keywords: N-Acetylsalicylic Acid ; Aspirin ; Pharmacokinetics ; Aging ; side effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of aspirin (ASA) has been studied in elderly Indians (〉 60 y) of either sex, composing, apparently healthy subjects controlled hypertensives and NIDDM diabetics, in comparison with healthy young subjects. Serum salicylate levels were estimated a 0, 0.5, 1, 2, 4 & 8 h after ASA. The pharmacokinetics of serum salicylate were not changed in elderly subjects as compared to the young after the first dose or after one week of ASA therapy, although greater variability was observed in the elderly. Various laboratory investigations were unaltered after one week in all the groups, except that one elderly hypertensive patient gained weight, and a young subject showed an increase in SGOT & SGPT.
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    URL: http://dx.doi.org/10.1007/BF00314810
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    Pharmacokinetics of melatonin in man after intravenous infusion and bolus injection (1990)
    Springer
    European journal of clinical pharmacology 38 (1990), S. 297-301 
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    ISSN: 1432-1041
    Keywords: Melatonin ; Pharmacokinetics ; replacement therapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of melatonin during the day-time has been studied in 4 healthy subjects after a bolus i.v. injection of 5 or 10 μg/person and after a 5 h infusion of 20 μg per person in 6 healthy subjects. In addition, a pinealomectomized patient whose nocturnal plasma melatonin had been abolished was investigated after the i. v. infusion — once during the night and once during the day. The clearance of melatonin from blood showed a biexponential decay. The pharmacokinetic parameters in the two studies were similar, except for the disappearance rate constant β and the apparent volume of distribution at steady-state (Vss). Supplementary peaks or troughs were superimposed on the plateau and the falling part of the profile. They were not due to stimulation of endogenous secretion, because they were also seen in the pinealomectomized patient. During the melatonin infusion, the plasma hormone level reached a steady-state after 60 and 120 min, and when it was equal to the nocturnal level. The infusion regime may be valuable in replacing blunted hormonal secretion in disease states.
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    URL: http://dx.doi.org/10.1007/BF00315035
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    Pharmacokinetics of midazolam in critically ill neonates (1990)
    Springer
    European journal of clinical pharmacology 39 (1990), S. 191-192 
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    ISSN: 1432-1041
    Keywords: Midazolam ; Neonates ; Pharmacokinetics ; Sedation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Midazolam is a water soluble benzodiazepine, with a short elimination half-life in adults and children. An IV bolus of midazolam 0.2 mg · kg−1 was administered to 10 critically ill neonates receiving intensive care who required sedation. The plasma clearance was 6.85 ml · min−1 and the elimination half-life was 6.52 h. Midazolam was well tolerated during and after administration. Because of its short half-life compared to diazepam, midazolam could be used during the neonatal period to produce brief rapid sedation.
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    URL: http://dx.doi.org/10.1007/BF00280059
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    Another Approach to the Modified Zhuravlev Equation on the Basis of the Oxidation of V2O4 and V6O13 (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 25-34 
    Details
    ISSN: 1572-8943
    Keywords: activation energy ; kinetic equation ; oxidation ; vanadium oxides ; Zhuravlev equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It has been found that the modified Zhuravlev equation, [(1−α)−1/3−1]2=ktn, which describes the kinetics of oxidation of V2O4 and V6O13 in the temperature range 820–900 K and in the oxygen pressure range 1.0–20 kPa, can be derived via the assumption that the changes in the observed activation energy result from the changing contributions of the two diffusion processes controlling the reaction rate. The values of the observed activation energy are in the range 160–175 kJ mol−1 for V2O4 and 188–201 kJ mol−1 for V6O13 in the scope of the experimental oxygen pressures and temperatures and conversion degrees of 0.1–0.9.
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    Empirical Relationships Describing Energetics of Adsorption at Low Coverages on Microporous Carbons (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 1011-1020 
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    ISSN: 1572-8943
    Keywords: adsorption ; adsorption calorimetry ; microporous carbon ; porosity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The fundamental empirical relationships that correlate the adsorption energy with physicochemical parameters of adsorbates are discussed. Based on the experimental data of the adsorption enthalpy of different organic adsorbates on microporous activated carbons some new correlations between adsorption enthalpy and entropy at zero surface coverage and physicochemical parameters of adsorbed molecules are proposed. It is shown that they can be applied for the calculation of carbon porosity. The influence of carbon surface oxidation on its energetic heterogeneity is also discussed.
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    Calorimetric Investigation of the Monolayers Formed At Solid-liquid Interface (1999)
    Springer
    Journal of thermal analysis and calorimetry 57 (1999), S. 643-651 
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    ISSN: 1572-8943
    Keywords: adsorption ; heat capacity ; solid-liquidinterface ; solid monolayer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Heat capacity measurements have been made to investigate the formation of two solid monolayers each of n-pentane, n-heptane and n-dodecane adsorbed on graphite, one at submonolayer coverages and the other coexisting with the liquid. At submonolayer coverages the monolayers are found to melt respectively at 99.8, 151.6, and 217.3 K, well below the bulk melting points. The monolayers coexisting with the liquid melted at 205.6 for heptane and at 287.8 K for dodecane, whereas no evidence was obtained for pentane on the formation of such solid monolayer above the bulk melting point. The order persisting in the liquid near the interface depends upon the length of the molecules. The dodecane monolayers showed another transitions below the melting points both at submonolayer and multilayer coverages.
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    Oxidation of Saturated Fatty Acids Esters DSC investigations (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 211-217 
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    ISSN: 1572-8943
    Keywords: DSC ; fatty acids esters ; kinetics ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidation of saturated fatty acids ethyl esters: laurate, myristate, palmitate and stearate was investigated by means of DSC techniques under isothermal and non-isothermal conditions. The activation energies of isothermal oxidation were similar to each other (112–123 kJ mol−1) and no influence of carbon length on the rate of oxidative decomposition was observed. Results obtained from non-isothermal experiments were similar only for the first stage of oxidation.
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    Calorimetric Investigation of Adsorption of Organic Compounds by Active Carbons (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 333-342 
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    ISSN: 1572-8943
    Keywords: active carbon ; adsorption ; enthalpies of wetting ; isothermal calorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Enthalpies of wetting of two active carbons and one brown coal coke by several pure liquids (mainly homologous series) were measured at 298.15 K with two quasi-isothermal microcalorimeters. Different measuring cells with cavities of about 0.5 and 15 cm3 were used. The advantage of the larger measuring cell with three independent 15 cm3 cavities is the higher mass of active carbon, leading to a high reproducibility with standard deviations below 1% and a reduced measuring time. Experiments were carried out with n-alkanes, l-alkanols, cycloalkanes and isomers thereof, i.e. 2-propanol, methylcyclohexane, 2,2,4-trimethylpentane (isooctane and 2-ethyl-1-hexanol, and water. Like the polarity, the size and the three-dimensional expansion of the molecules, the energetic and geometric heterogeneity of the adsorbent influences the enthalpy of wetting.
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    Comparison of Sorptometric and Thermoporometric Measurements on Porous Glass and Some Others (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 323-330 
    Details
    ISSN: 1572-8943
    Keywords: adsorption ; balance ; gravimetry ; sorption ; thermoporometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The results of surface structure investigations involving the use of thermoporometry and gas-sorptometry on porous glass, silica and a zeolite were compared. The most frequent and the mean pore width were found to be in accordance, but major differences in specific surface were observed. These two measuring methods complement each other, because with gas adsorption a dry sample is investigated, while with thermoporometry a sample immersed in a liquid is investigated. The probe molecules (nitrogen or noble gas and water or benzene, respectively) differ in size. The features of the two methods are discussed.
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    Charge Transfer Between Oxygen and Zirconia (1999)
    Springer
    Journal of thermal analysis and calorimetry 57 (1999), S. 875-881 
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    ISSN: 1572-8943
    Keywords: charge transfer ; Kelvin probe ; oxidation ; work function ; zirconia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The extent of the surface charge, that develops during oxidation of zirconia, is determined using work function measurements for both bulk specimen and thin films. The bulk specimen of yttria-doped zirconia (10 mol%) exhibits maxima of the surface electrical effect at 373 and 973 K (130 and 280 mV, respectively) that can be considered in terms of oxygen chemisorption and oxygen non-stoichiometry. Thin film of undoped zirconia exhibits a maximum at 473 K (260 eV). Addition of yttria (10 mol%) to the thin film results in a substantial reduction of the maximum, to about 140 eV, that is shifted up to 600 K.
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    Derivative Enthalpies of Adsorption of p-Xylene and m-xylene onto NaY and BaY Zeolites at 150°C: Contribution to the prediction of adsorption selectivity (1999)
    Springer
    Journal of thermal analysis and calorimetry 58 (1999), S. 121-128 
    Details
    ISSN: 1572-8943
    Keywords: adsorption ; calorimetry ; derivative enthalpy ; prediction ; selectivity ; single xylene ; xylene mixture ; zeolite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The derivative enthalpies of adsorption of m-xylene and p-xylene onto the NaY and BaY zeolites were measured at 150°C, then compared with those obtained at 25°C, and finally used to predict the selectivity of adsorption of xylene mixtures. Significant differences were observed as the temperature was elevated: for the NaY zeolite, the adsorbate-adsorbate interactions became prevalent, in contrast with the BaY zeolite, between zeolite and derivative interactions were stronger. The difference between the adsorption derivative enthalpies of the two xylenes displayed an abrupt variation from 2 molec. α−1 for both zeolites, the filling from which selectivity towards m-xylene for the NaY zeolite and towards p-xylene for the BaY zeolite appeared. The preferentially adsorbed xylene was closely connected with the sense of this difference, which changed with the zeolite.
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    Comportement Thermique du Polypropylene au Cours du Vieillissement (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 327-340 
    Details
    ISSN: 1572-8943
    Keywords: aging ; DTA-TG ; oxidation ; polypropylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Several samples of polypropylene were studied by thermal analysis. The photo-oxidation and the aging of polypropylene films showed a mass loss more than 7% in heating from 20 to 220°C (5°C min-1), cooling to 20°C and reheating to 220°C. The authors observed also a decrease of the melting and crystallization temperatures. The non aged samples or these ones with preservatives are thermo-oxidised and presented an exothermic peak at about 200°C in DTA heating. The DTA-TG simultaneous apparatus is very useful in the study of polypropylene oxidation by making comparative trials according to a well definite procedure.
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    Kinetics and Mechanism of the Oxidation of Molybdenum Sulphide (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 263-267 
    Details
    ISSN: 1572-8943
    Keywords: kinetics ; molybdenum sulphide ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper reports on the results attained in the determination of the mechanism of oxidation of molybdenum sulphide under non-isothermal conditions in an air atmosphere. The mechanism of the process was determined by simultaneous DTA-TG-DTG, and the kinetic parameters of the reactions involved were obtained according to the methods of Kissinger and Ozawa.
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    URL: http://dx.doi.org/10.1023/A:1010108813595
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    Etude de L'oxydation de Polyethylenes Par Analyse Thermique Identification des produits de dégradation par infra-rouge (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 923-930 
    Details
    ISSN: 1572-8943
    Keywords: DSC ; infrared spectrometry ; oxidation ; polyethylenes ; thermal analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of pure and recycled polyethylene samples was studied by thermal analysis (DTA-TG-DSC): presence of two exothermic peaks and mass loss. The thermo-oxidation products, containing C-O and C=O links, were identified by IR spectrometry and GC-MS spectrometry. The oxidation is easier from low to high density polyethylene.
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    Thermodynamics of Adsorption on Microporous Fractal Solids (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 351-361 
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    ISSN: 1572-8943
    Keywords: active carbon ; adsorption ; adsorption thermodynamics ; fractal dimension ; microporosity ; pore diameter ; potential theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new adsorption isotherm equation based on the extension of the potential theory of adsorption on microporous fractal solids and corresponding thermodynamic functions were formulated and applied for description of the experimental data of adsorption on a microporous carbon. The comparison of the obtained results with the original Dubinin-Astakhov equation is presented. In this paper the dependence of thermodynamic functions (the differential molar enthalpy of adsorption ΔH and the differential molar entropy of adsorption ΔS) on the fractal dimension D are discussed, as well.
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    Inhibited Oxidation of Cumene and Polymerization of Styrene Investigated by Solution Microcalorimetry (1999)
    Springer
    Journal of thermal analysis and calorimetry 57 (1999), S. 473-486 
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    ISSN: 1572-8943
    Keywords: cumene ; oxidation ; polymerization ; quinone-amine inhibitors ; solution microcalorimetry ; styrene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of solution microcalorimetry was demonstrated on two model examples – inhibited oxidation of cumene and radical polymerization of styrene. From the experimental dependences of the rate of heat release on time, the rate constants k 7 of the interaction of an inhibitor with radicals of substrate (RO 2 . or R.) in oxidation or in polymerization were determined for the set of inhibitors of N-aryl N-(2-quinone) amine series. It was shown that these compounds are weak inhibitors of oxidation of cumene and rather efficient inhibitor of polymerization of styrene.
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    URL: http://dx.doi.org/10.1023/A:1010116024873
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    Thermogravimetric Analysis of γ-Aminopropyl-trimethoxysilane Adsorbed on Silica Support (1999)
    Springer
    Journal of thermal analysis and calorimetry 58 (1999), S. 67-76 
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    ISSN: 1572-8943
    Keywords: adsorption ; DRIFT spectroscopy ; elemental analysis ; γ-aminopropyl-trimethoxysilane ; thermogravimetric analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A comparative method based on thermogravimetry is applied in order to characterise chemically functionalised surfaces. The mass loss of silica modified with γ-aminopropyl-trimethoxysilane (γ-APS) adsorbed from a range of solvents is interpreted by considering the physically adsorbed water, the silanol groups and the organic solvent. DRIFT spectroscopy is used to analyse the binding structure and adsorption mechanism. The mass loss calculated from thermogravimetric analysis is found to be in agreement with the values obtained by classical elemental analysis. Thermogravimetric analysis is found to be a quick and reproducible method, which only requires a few milligram sample. The amount adsorbed seems to be primarily dependent on the solvation of the γ-aminopropyl-trimethoxysilane by the solvent. A good solvent prevents adsorption as shown when comparing the magnitude of the mass loss with the difference between the solubility parameters of the γ-APS and the solvents. Ethanol seems to influence the structure of the adsorbed γ-aminopropyl-trimethoxysilane film.
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    Tetrachlorosilane Consumption in Radio Frequency Glow Discharge (1998)
    Springer
    Plasma chemistry and plasma processing 18 (1998), S. 509-533 
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    ISSN: 1572-8986
    Keywords: RF SiCl4 discharge ; mass spectrometry ; kinetics ; decomposition ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Time-resolved mass spectrometry was used for analysis of the plasma reactions in radio frequency (RF) SiCl 4 and SiCl 4 −O 2 discharges as functions of starting partial pressure and electrical power. Molecular concentrations of the reactants and products from SiCl 4 alone and with O 2 were obtained from the mass spectra and used for plotting the kinetic curves. The SiCl 4 and O 2 consumption rates were calculated from the kinetic curves and compared with results of theoretical simulation of the reaction. Direct electron impact decomposition was found to be the main pathway for pure SiCl 4 conversion. On the contrary, the consumption of SiCl 4 in the SiCl 4 +O 2 mixtures was largely chemical. The experimental macrokinetics are in agreement with a model in which oxidation is caused by the atomic oxygen.
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    Oxidation of Styrene in a Silent Discharge Plasma (1999)
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    Plasma chemistry and plasma processing 19 (1999), S. 131-151 
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    ISSN: 1572-8986
    Keywords: Styrene ; oxidation ; silent discharge ; plasma ; dielectric barrier
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract A silent discharge plasma reactor has been developed to study the oxidation of styrene vapor in argon/oxygen mixtures. A number of analytical techniques were employed to determine the destruction efficiency and to characterize the intermediate products. The destruction efficiency was measured as a function of initial styrene concentration, temperature, and energy density of the plasma. The formation of solid products was observed in most experiments. At low temperature (100°C), the solid deposit was polymeric in nature, while at high temperature (300°C) the solid appeared to be amorphous carbon. A combination of high temperature and high energy density resulted in high destruction efficiency and minimal production of solid films. The destruction efficiency vs. energy density is shown to be more complex than a simple model predicting exponential behavior. Several reasons for the discrepancy are suggested. The “e-folding” energy density for the destruction of styrene is compared to literature values for other organic compounds, measured using similar types of plasma reactors.
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    Oxidation of Dilute Benzene in an Alumina Hybrid Plasma Reactor at Atmospheric Pressure (1999)
    Springer
    Plasma chemistry and plasma processing 19 (1999), S. 383-394 
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    ISSN: 1572-8986
    Keywords: Nonthermal plasma ; benzene ; Al2O3 ; BaTiO3 ; oxidation ; absorption ; atmospheric pressure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The combination of plasma discharge and adsorption was examined for oxidation of dilute benzene in air in a plasma reactor packed with a mixture of BaTiO 3 pellets and porous Al 2 O 3 pellets (i.e., an alumina hybrid reactor). The oxidative decomposition of benzene was enhanced by the benzene concentrating on the Al 2 O 3 pellets. Furthermore, there was a higher selectivity to CO 2 in the products from the hybrid than from a plasma reactor packed with BaTiO 3 pellets alone. The presence of the Al 2 O 3 pellets suppressed the formation of N 2 O.
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    Oxidation and Reduction Processes During NO x Removal with Corona-Induced Nonthermal Plasma (1999)
    Springer
    Plasma chemistry and plasma processing 19 (1999), S. 421-443 
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    ISSN: 1572-8986
    Keywords: Streamer corona ; NO x removal ; nonthermal plasma ; oxidation ; reduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract In this paper, the NO-to-NO 2 conversion in various gaseous mixtures is experimentally investigated. Streamer coronas are produced with a dc-superimposed high-frequency ac power supply (10–60 kHz). According to NO x removal experiments in N 2 +NO x and N 2 +O 2 +NO x gaseous mixtures, it is supposed that the reverse reaction NO 2 +O→NO+O 2 may not only limit NO 2 production in N 2 +NO x mixtures, but also increase the energy cost for NO removal. Oxygen could significantly suppress reduction reactions and enhance oxidation processes. The reduction reactions, such as N+NO→N 2 +O, induce negligible NO removal provided the O 2 concentration is larger than 3.6%. With adding H 2 O into the reactor, the produced NO 2 per unit removed NO can be significantly reduced due to NO 2 oxidation. NH 3 injection could also significantly decrease the produced NO 2 via NH and NH 2 - related reduction reactions. Almost 100% of NO 2 can be removed in gaseous mixtures of N 2 +O 2 +H 2 O+NO 2 with negligible NO production.
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    Yttrium Acetate-Derived Particle Coatings for Mitigating Oxidation and Corrosion of Inconel 625 (1998)
    Springer
    Journal of sol gel science and technology 12 (1998), S. 35-48 
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    ISSN: 1573-4846
    Keywords: yttrium acetate precursor ; particle coating ; oxidation ; corrosion ; Inconel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract “Sol paint” that yields yttrium-based compounds was prepared by mixing four chemical ingredients, yttrium acetate tetrahydrate precursor, diethanolamine, isopropyl alcohol, and hydrochloric acid, and then applied as oxidation/corrosion resistant coatings for Inconel 625 substrates. Annealing the coatings at 500°C developed a coalescent microstructure of coarse particles consisting of amorphous yttrium carbonate as the major component and crystalline yttrium oxide (Y2O3) as the minor one. At 700°C, the yttrium carbonate was transformed into Y2O3 by decarbonation. Increasing the annealing temperature to 900°C led to the formation of the YCrO3 phase yielded by interaction between Y2O3 and the Cr2O3 which had arisen from the oxidation of the underlying Inconel; the YCrO3 phase created a particle coating with a densified microstructure. There were two key factors in mitigating the degree of oxidation of Inconel at 900°C in air: (1) an uptake of oxygen by Y2O3 in the coatings, and (2) a densified coating layer that suppresses the diffusion and permeation of oxygen through it. Furthermore, inhibiting the rate of NaCl-caused corrosion was not only due to the excellent coverage of particle coatings over the entire surfaces of the substrates, but also may be associated with a good adherence of the coatings to the substrates.
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    Sol-Gel Synthesis and Gas Adsorption Properties of CuCl Modified Mesoporous Alumina (1998)
    Springer
    Journal of sol gel science and technology 11 (1998), S. 185-195 
    Details
    ISSN: 1573-4846
    Keywords: cuprous chloride ; gamma-alumina ; adsorption ; ethylene ; carbon monoxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cuprous chloride (CuCl) modified unsupported γ-alumina membranes and adsorbent granules were synthesized by sol-gel processing followed by wet-impregnation of CuCl. The CuCl coated γ-alumina remains mesoporous with a uniform pore size distribution and a large surface area. The mesoporous alumina granules, prepared by a sol-gel oil-drop process, exhibit excellent mechanical strength and attrition resistance. The CuCl modified γ-alumina preferentially adsorbs ethylene and carbon monoxide, with a saturated adsorption capacity of 0.67 and 0.78 mmol/g, respectively. Both equilibrium capacity and kinetic rate for adsorption of ethylene and carbon monoxide on the CuCl modified γ-alumina are much larger than those for ethane and carbon dioxide. These results indicate the potential use of the sol-gel derived CuCl modified γ-alumina for separation of ethylene or carbon monoxide from its gas mixture containing ethane or carbon dioxide.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008601715782
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  • 97
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    An in vitro study on the role of metal catalyzed oxidation in glyeation and crosslinking of collagen (1999)
    Springer
    Molecular and cellular biochemistry 194 (1999), S. 257-263 
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    ISSN: 1573-4919
    Keywords: glycation ; oxidation ; collagen ; diabetes ; free radicals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The present investigation was carried out to understand the effect of metal catalyzed oxidation on glycation and crosslinking of collagen. Tail tendons obtained from rats weighing 200-225 g were incubated with glucose (250 mM) and increasing concentrations of copper ions (5, 25, 50 and 100 μM) under physiological conditions of temperature and pH. Early glycation, crosslinking and late glycation (fluorescence) of collagen samples were analyzed periodically. Early glycation was estimated by phenol sulfuric acid method, and the crosslinking was assessed by pepsin and cyanogen bromide digestion. A concentrationdependent effect of metal ions on the rate of glycation and crosslinking of collagen was observed. Tendon collagen incubated with glucose and 100 μM copper ions showed 80% reduction in pepsin digestion within seven days, indicating extensive crosslinking, whereas collagen incubated with glucose alone for the same period showed only 7% reduction. The presence of metal ions in the incubation medium accelerated the development of Maillard reaction fluorescence on collagen, and the increase was dependent on the concentration of metal ions used. The metal chelator Diethylene triamine penta-acetate significantly prevented the increase in collagen crosslinking by glucose and copper ions. Free radical scavengers benzoate and mannitol effectively prevented the increased crosslinking and browning of collagen by glucose. The results indicate that the metal catalyzed oxidation reactions play a major role in the crosslinking of collagen by glucose. It is also suggested that the prevention of increased oxidative stress in diabetes may prevent the accelerated advanced glycation and crosslinking of collagen.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1006988719374
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  • 98
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    Electronic Resource
    Production of interleukin-1β by periodic acid-oxidized human peripheral blood mononuclear cells (1990)
    Springer
    Molecular and cellular biochemistry 95 (1990), S. 177-182 
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    ISSN: 1573-4919
    Keywords: periodate ; oxidation ; membrane ; cells ; interleukin-1
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Interleukin-1 (IL-1) production by periodic acid (H5IO6)-oxidized human peripheral blood mononuclear (PBMN) cells was assessed by the thymocyte co-mitogenesis assay. Maximum IL-1 levels (∼ 1.2 U/ml) in the conditioned media of PBMN cells were registered within the first 24 hrs post-oxidation, whereas no IL-1 was detected in the media from 24 hrs control cultures. Thymocyte proliferation, driven by periodic acid-induced IL-1, was abolished by an antibody to IL-1alpha and IL-1β. Quantitative analysis of IL-1-containing medium by radioimmunoassay (RIA) indicated that IL-1β comprised about 80% of total IL-1. Partial characterization of H5IO6-induced IL-1β indicated that it was identical to IL-1 produced by lipopolysaccharide-stimulated macrophages. It is concluded that oxidation of human PBMN cells by H5IO6 triggers synthesis and release of IL-1, most of which was in its IL-1β form.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00219976
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  • 99
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    Electronic Resource
    Attenuation of sugar cataract by ethyl pyruvate (1999)
    Springer
    Molecular and cellular biochemistry 200 (1999), S. 103-109 
    Details
    ISSN: 1573-4919
    Keywords: sugar cataract ; dulcitol ; glycation ; oxidation ; pyruvate ; ethyl pyruvate ; attenuation effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Studies describe an attenuation of sugar cataract formation by topical administration of ethyl pyruvate. Cataract formation was induced by feeding young rats a 30% galactose diet. Mature cataracts appeared in about thirty days. Instillation of the eye drops containing 5% ethyl pyruvate decelerated the process significantly. Biochemically, the effect was reflected by lowering in the contents of dulcitol and glycated proteins. The ATP levels were also higher in comparison to the placebo treated group. The effects are hence attributable to the effect of pyruvate in inhibiting dulcitol synthesis and protein glycation, in addition to its antioxidant properties and metabolic support. The use of esterified pyruvate instead of the unesterified pyruvate was preferred because of its greater penetration through the cornea and consequently a higher concentration attained in the aqueous humor.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007055503748
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  • 100
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    Ellipsometric study of a palladium catalyst during the oxidation of carbon monoxide and methane (1999)
    Springer
    Topics in catalysis 8 (1999), S. 35-43 
    Details
    ISSN: 1572-9028
    Keywords: ellipsometry ; carbon monoxide ; methane ; palladium ; palladium oxide ; oxidation ; oscillations ; catalyst
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Spectroscopic ellipsometry is used to monitor the surface of a thick Pd‐film catalyst during the oxidation of either carbon monoxide or methane. Dense PdO layers form under sufficiently lean conditions (excess oxygen) for both reactions. A stable metal surface exists in the case of CO, but a very porous PdO layer develops in the case of methane, under rich conditions. There is a large hysteresis in the conditions for PdO formation in the case of CO oxidation. Spontaneous oscillations in catalytic activity and Pd‐surface composition occur for both reactions, the higher activities corresponding to O‐atom‐rich or PdO‐rich surfaces for CO or methane oxidation, respectively.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019128203919
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