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  • 1
    ISSN: 1040-0397
    Keywords: Chromium ; Microelectrodes ; Adsorptive stripping voltammetry ; Biomaterials ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chromium is the metallic species of most concern with the use of stainless steel implants. To study the distribution of chromium in mice organs with time, several animals were subcutaneously injected with 2.70 × 10-3 mol/L of chromium solution during a certain period of time. Square wave voltammetry using adsorptive collection of Cr3+ -DTPA complex on a mercury film microelectrode (MFM) was used for quantitation. Optimized conditions included DTPA concentration of 2.0 × 10-2 mol/L, sodium acetate 4.0 × 10-2 mol/L, sodium nitrate 0.40 mol/L, potassium permanganate 1.0 × 10-3 mol/L, pH ca. 6.1, deposition potential of -1.15 V, deposition time 20 s, frequency 100 Hz, step 2.5 mV and an amplitude of 20 mV. The detection limit of the method was 1.54 × 10-8 mol/L after deposition of 20s. Other species presented in the biological material such as calcium and iron do not interfere with the chromium determinations. The accuracy of the proposed method was checked by comparing the results with those obtained by atomic absorption spectrometry (AAS) yielding good agreement. The results showed an increase of chromium levels with time in liver, kidney and spleen, indicating that this metal is partially accumulated in the studied organs.
    Additional Material: 3 Ill.
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  • 2
    ISSN: 0935-6304
    Keywords: high temperature gas chromatography ; flavonoids ; propolis ; high molecular weight compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The underivatized acetone and hexane fractions from propolis samples (predominant flora Citrus spp. and Vernonia polyanthes) were analyzed by HT-HRGC (high temperature high resolution gas chromatography) and HT-HRGC coupled to mass spectrometry (HT-HRGC-MS). Several compounds, including flavonoid aglycones, phenolic acids, and high molecular weight compounds were characterized in crude extracts by HT-HRGC-MS. HT-HRGC and HT-HRGC-MS were shown to be quick and informative tools for rapid analysis of crude extracts without need for prior derivatization and purification.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 40 (1998), S. 40-47 
    ISSN: 0021-9304
    Keywords: nickel ; biomaterial ; mice ; microelectrodes ; histology ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: The toxic effects caused by nickel (Ni) per si were explored by performing in vivo studies on mice following subcutaneous administration of a metallic solution of nickel at 1, 2, 3, and 4 weeks to evaluate the side effects of this metal ion when released from stainless steel implants. Other groups were similarly injected with HBSS and used as controls. Accumulation of Ni ions on liver, spleen, and kidney was assessed by an electrochemical method, adsorptive stripping voltammetry (AdSV) using microelectrodes, and atomic absorption spectrometry (AAS). Alterations of those organs induced by Ni ions were studied, showing that several histological changes had been induced. Chemical analysis and histological features indicate that Ni is partially accumulated in the study organs. © 1998 John Wiley & Sons, Inc. J Biomed Mater Res, 40, 40-47, 1998.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 25 (1979), S. 1036-1043 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The commonly employed internal isothermal model for gas-solid catalytic reactions, wherein the pellet is assumed internally isothermal but with internal concentration gradient, is justified by analyzing the full non-isothermal diffusion-reaction equations as an appropriate perturbation problem (β small, and Bih/β finite). The internal isothermal model is shown to be the zeroth order solution of the perturbation problem. Analytic expressions for the first order corrections are given for a first order reaction.
    Additional Material: 6 Ill.
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  • 5
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Microkinetic simulations have been carried out to describe the partial oxidation of methane over silica-supported molybdena and vanadia. The objective of this study was to formulate a physically reasonable reaction network to capture the basic aspects of the surface catalytic chemistry and to use this network to link methane oxidation kinetics with the kinetics observed for the oxidation of subsequent gaseous products, i.e., methanol, formaldehyde, and carbon monoxide. The most abundant reactive intermediates on the catalyst surface are suggested to be oxygen and hydroxyl groups. This reaction network successfully predicts the catalytic activities, selectivities, activation energies, and reaction orders observed over silica-supported molybdena and vanadia; and the microkinetic model also semiquantitatively explains the kinetic trends for related catalyst systems and is consistent with surface bonding energetics reported in the literature over various oxide catalysts. The microkinetic reaction network properly reduces to the more simple macrokinetic model reported previously for methane partial oxidation.
    Additional Material: 12 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 36 (1990), S. 559-564 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The diffusion of 1,3,5 tri-tert-butylbenzene (TTB) into cylindrical γ-alumina extrudates of varying micropore diameter and macropore volume has been studied by NMR spectroscopy. The proton NMR signal of the methyl proton of TTB in the micropores of the alumina extrudate was found to be well resolved and shifted upfield relative to that in the bulk liquid by 0.55 ppm. The area under the shifted peak is proportional to the liquid concentration of TTB in the micropores. The change in the intensity of this peak as a function of time and measurements of the amount of TTB absorbed on the surface alumina at equilibrium were used to calculate the effective diffusivity of TTB in each extrudate. Measured values of the effective diffusivity are in reasonable agreement with predictions using correlations in the literature. These observations suggest a new method for measuring the liquid-phase effective diffusivity in porous materials.
    Additional Material: 8 Ill.
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  • 7
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 33 (1987), S. 1808-1812 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: There is considerable economic incentive to convert methane into formaldehyde, which is used in the manufacture of insulating materials and adhesives. This paper discusses the kinetics of a one-step oxidation of methane with molecular oxygen over a MoO3-SiO2 catalyst. The space velocity was varied between 2,500 and 10,000 h-1 (at NTP) over a range of temperatures from 848 to 923 K.Selectivities to formaldehyde between 30 and 89% were observed in the 0-5% methane conversion range, the other principal products being CO, CO2, and H2O. Kinetic analysis indicates that methane is directly oxidized to CO2 and HCHO, with HCHO being further oxidized to CO. The reactions were all found to be zero order in oxygen concentration, with methane and formaldehyde oxidation following overall first-order rate laws. Kinetic rate constants have been determined and there is good agreement between model predictions and experimental data.
    Additional Material: 8 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 57 (1998), S. 610-619 
    ISSN: 0006-3592
    Keywords: dynamic model ; Saccharomyces cerevisiae ; oxidative capacity ; feedback control ; calorimetry ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The objective of this study was to characterize the dynamic adaptation of the oxidative capacity of Saccharomyces cerevisiae to an increase in the glucose supply rate and its implications for the control of a continuous culture designed to produce biomass without allowing glucose to be diverted into the reductive metabolism. Continuous cultures subjected to a sudden shift-up in the dilution rate showed that the glucose uptake rate increased immediately to the new feeding rate but that the oxygen consumption could not follow fast enough to ensure a completely oxidative metabolism. Thus, part of the glucose assimilated was degraded by the reductive metabolism, resulting in a temporary decrease of biomass concentration, even if the final dilution rate was below Dcrit. The dynamic increase of the specific oxygen consumption rate, qO2, was characterized by an initial immediate jump followed by a first-order increase to the maximum value. It could be modeled using three parameters denoted qjumpO2, qmaxO2, and a time constant τ. The values for the first two of the parameters varied considerably from one shift to another, even when they were performed under identical conditions. On the basis of this model, a time-dependent feed flow rate function was derived that should permit an increase in the dilution rate from one value to another without provoking the appearance of reductive metabolism. The idea was to increase the glucose supply in parallel with the dynamic increase of the oxidative capacity of the culture, so that all of the assimilated glucose could always be oxidized. Nevertheless, corresponding feed-profile experiments showed that deviations in the reductive metabolism could not be completely suppressed due to variability in the model parameters. Therefore, a proportional feedback controller using heat evolution rate measurements was implemented. Calorimetry provides an excellent and rapid estimate of the metabolic activity. Satisfactory control was achieved and led to constant biomass yields. Ethanol accumulated only up to 0.49 g L-1 as compared to an accumulation of 1.82 g L-1 without on-line control in the shift-up experiment to the same final dilution rate. ©1998 John Wiley & Sons, Inc. Biotechnol Bioeng 57: 610-619, 1998.
    Additional Material: 9 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 48 (1995), S. 246-256 
    ISSN: 0006-3592
    Keywords: polyethylene glycol ; phosphate ; phase separation ; kinetics ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Phase separation times for polyethylene glycol (PEG)-4000-phosphate aqueous two-phase systems were studied, for small scale (5-g) and large scale (1300-g) systems, as a -function of the stability ratio. Profiles of dispersion height for both large and small scale systems were represented as a fraction of the initial height and were found to be independent of the geometrical dimensions of the separator. Furthermore, by plotting time as a fraction of the initial height the total time of separation can be calculated for a given height of system at a particular stability ratio. This generalization is important for the design of large scale aqueous two-phase separators. Phase separation times were also found to be dependent on which of the phases is continuous. A characteristic change in phase separation time was also observed at the phase inversion point (i.e., where the dispersed phase changes to a continuous phase and vice versa) and this point tends toward higher volume ratios as the tie-line length (TLL) is increased. Furthermore, the phase inversion point at each TLL corresponds to a fixed phosphate concentration. © 1995 John Wiley & Sons, Inc.
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