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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1138-1155 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Effects of hard constraints in the stability of model-perdictive control (MPC) are reviewed. Assuming a fixed active set, the optimal solution can be expressed in a general state-feedback closed form, which corresponds to a piecewise linear controller for the linear model case. Changes in the original unconstrained solution by the active constraints and other effects related to the loss of degrees of freedom are depicted in this analysis. In addition to modifications in the unconstrained feedback gain, we show that the presence of active output constraints can introduce extra feedback terms in the predictive controller. This can lead to instability of the constrained closed-loop system with certain active sets, independent of the choice of tuning parameters. To cope with these problems and extend the constraint handling capabilities of MPC, we introduce the consideration of soft constraints. We compare the use of the l2-(quadratic), l1-(exact), and l∞-norm penalty formulations. The analysis reveals a strong similarity between the control laws, which allows a direct extrapolation of the unconstrained tuning guidelines to the constrained case. In particular, the exact penalty treatment has identical stability characteristics to the correspondent unconstrained case and therefore seems well suited for general soft constraint handling, even with nonlinear models. These extensions are included in the previously developed Newton control framework, allowing the use of the approach within a consistent framework for both linear and nonlinear process models, increasing the scope of applications of the method. Process examples illustrate the capabilities of the proposed approaches.
    Additional Material: 12 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 33 (1989), S. 1324-1329 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 8 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 41 (1990), S. 736-742 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Einfluß von Temperatur und Gaszusammensetzung auf das Korrosionsverhalten von Siliciumnitrid in sulfidierenden Atmosphären mit niedrigem SauerstoffpotentialÜber das Verhalten der neuen Siliciumnitridkeramiken in reduzierenden Atmosphären (z. B. bei der Kohlevergasung oder in petrochemischen Anlagen) ist wenig bekannt. In solchen Atmosphären mit niedrigem Sauerstoffpotential, die Schwefel enthalten, treten neben dem flüchtigen Siliciummonoxid auch flüchtige Siliciumsulfide auf, wodurch die Korrosion beschleunigt wird. Zur Darstellung dieser Verhältnisse wird eine „Flüchtigkeitskarte“ entwickelt, die die Verhältnisse in solchen Gasen bei 1200 und 1300°C zeigt: dabei sind die Partialdrucke von SiO und SiS (im Gleichgewicht mit Si oder SiO2) in Abhängigkeit von Sauerstoffund Schwefelpartialdrucken aufgetragen. Dabei ergeben sich unterschiedliche Korrosionsbereiche: wenn SiO2 nicht stabil ist und hohe SiS-V Partialdrucke zu erwarten sind, kann die Korrosion katastrophal werden; ist SiO2 stabil, so verhindert die glasartige Schicht zunächst die Verdampfung von SiS, doch wird sie allmählich in SiO umgewandelt, und hohe SiS-Partialdrucke können zu innerer Sulfidierung führen.
    Notes: Little is known about the behaviour of advanced silicon nitride materials in reducing atmospheres (e.g. in coal gasification or in petrochemical plant). In such atmospheres with low oxygen potential and containing sulphur volatile silicon sulphides are formed in addition to the volatile silicon oxide, so that corrosion would be accelerated. In order to graphically represent these conditions a “volatility map” is presented which shows the conditions in such atmospheres at 1200 and 1300°C; the map shows the partial pressures of SiO and SiS (in equilibrium with Si or SiO2) vs oxygen and sulphur partial pressures. The map shows various corrosion regions: when SiO2 is not stable and high SiS partial pressures are predicted, corrosion may be catastrophic; when SiO2 is stable, the glassy surface layer initially prevents evaporation of SiS which, however, is gradually transformed into SiO, and high SiS partial pressures may result in internal sulphidation.
    Additional Material: 10 Ill.
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  • 4
    ISSN: 1040-0397
    Keywords: Carboplatin ; DNA ; Anticancer drug ; Modified electrode ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An electrochemical method for the determination of the anticancer platinum drug carboplatin using a DNA-modified electrode was developed. This electrode was successfully used for the electrochemical determination of carboplatin in serum samples of patients with ovarian cancer undergoing treatment. The electrochemical results clearly demonstrated that, for low concentrations, carboplatin interacts preferentially with adenine rather than guanine groups in the DNA and they can contribute to clarifying the mechanisms of interaction of platinum anticancer drugs with DNA. The pharmacokinetics corresponding to the administration of the drug was followed electrochemically and the detection limit in serum samples was 5.7 × 10 -6M. Due to a similar mechanism of reaction with DNA other platinum anticancer drugs can be determined by this method.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 12 (1998), S. 591-599 
    ISSN: 0268-2605
    Keywords: arsenic speciation ; LC-ICP-MS ; validation ; urine samples ; background levels ; The Netherlands ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method validation for the speciation of five arsenic species in urine samples by liquid chromatography hyphenated to inductively coupled plasma mass spectrometry is described. Arsenic species which are identified and quantified in urine samples are the anions of arsenic(III), arsenic(V), monomethylarsonic acid and dimethylarsinic acid, and the cationic arsenobetaine. Detection limits were obtained in the range 0.3-0.4 μg As l-1 while the repeatability was in the range 3-4% (RSD) for concentrations above five times the detection limit. Urine samples could be analysed directly after a ten-fold dilution step. Arsenic compound concentrations were determined in urine samples from a volunteer who consumed a portion of tuna fish high in arsenobetaine. It was found that arsenobetaine was excreted rapidly via the urine with maximum concentrations after 12 h. Nearly complete arsenobetaine excretion was reached after 48 h. Background levels of arsenic compounds were determined in 61 urine samples from non-exposed inhabitants of The Netherlands. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 19 (1998), S. 524-534 
    ISSN: 0192-8651
    Keywords: ab initio conformational analysis ; cyclooctane molecule ; potential energy surface ; Hartree-Fock theory ; Møller-Plesset theory ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The potential energy surface (PES) for the cyclooctane molecule was comprehensively investigated at the Hartree-Fock (HF) level of theory employing the 3-21G, 6-31G, and 6-31G* basis sets. Six distinct true minimum energy structures (named B, BB, BC, CROWN, TBC, and TCC1), characterized through harmonic frequency analysis, were located on the multidimensional PES. Two transition state structures were also located on the PES for the cyclooctane molecule. Electron correlation effects were accounted for using the Møller-Plesset second-order perturbation theory (MP2) approach. The predicted global minimum energy structure on the ab initio PES for the cyclooctane molecule is the BC conformer. A gas phase electron diffraction study at 300 K suggested a conformational mixture while an NMR study in solution at 161.5 K predicted the BC conformer as the predominant form. The equilibrium constants reported in the present study, which were evaluated from the ab initio calculated total Gibbs free energy change values, were in good agreement with both experimental investigations. The ab initio results showed that the low temperature condition significantly favored the BC conformer while above room temperature both BC and CROWN structures can coexist.   © 1998 John Wiley & Sons, Inc.   J Comput Chem 19: 524-534, 1998
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 17 (1996), S. 167-177 
    ISSN: 0192-8651
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Factorial design and principal component analyses are applied to CH3F infrared frequencies and intensities calculated from ab initio wave functions. In the factorial analysis, the quantitative effects of changing from a 6-31G to a 6-311G basis, of including polarization and diffuse orbitals, and of correcting for electron correlation using the second-order Møller-Plesset procedure are determined for all frequencies and intensities. The most significant main effect observed for the frequencies corresponds to the shift from Hartree-Fock to MP2 calculations, which tends to lower all frequency values by approximately 100 cm-1. For the intensities, the main effects are larger for the CF stretching and the CH3 asymmetric stretching modes. Interaction effects between two or more of the four factors are found to be of minor importance, except for the interaction between correlation and polarization. The principal component analysis indicates that wave functions with polarization and diffuse orbitals at the second-order Møller-Plesset level provide the best estimates for the harmonic frequencies, but not for the intensities. For the frequencies, the first principal component distinguishes between MP2 and Hartree-Fock calculations, while the second component separates the wave functions with polarization orbitals from those without these orbitals. For the intensities, the separation is similar but less well defined. This analysis also shows that wave function optimization to calculate accurate intensities is more difficult than an optimization for frequencies. © 1996 by John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 8
    ISSN: 0263-6484
    Keywords: HeLa cells ; methotrexate ; anticancer ; transplasma electron transport ; ferricyanide-induced proton extrusion ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The effect of methotrexate (MTX) on transplasma-membrane electron transport and ferricyanide-induced proton extrusion by HeLa cells was studied. Both systems were inhibited by MTX. It is suggested that inhibition of electron transport and proton extrusion caused by MTX could be associated with other metabolic alterations such as response to the increase in NADH levels and decrease in intracellular pH.
    Additional Material: 2 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Cell Biochemistry and Function 13 (1995), S. 53-59 
    ISSN: 0263-6484
    Keywords: Kidney cortex and liver mitochondria ; BHK-21 cultured cells ; 2-oxoglutarate and pyruvate dehydrogenases ; calcium transport ; citrinin ; mycotoxin ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The effect of citrinin on Ca2+ transport was studied in isolated kidney cortex and liver mitochondria, and baby hamster kidney cultured cells. The mycotoxin significantly inhibited the activity of 2-oxoglutarate and pyruvate dehydrogenases in both kidney cortex and liver mitochondria. Citrinin promoted a decrease in the velocity and in the total capacity of Ca2+ uptake, in both mitochondria. Apparently, citrinin acts by a mechanism similar to ruthenium red. In intact cultured cells, citrinin also had a preferential effect on mitochondrial Ca2+ fluxes. Citrinin promoted a marked decrease in the Ca2+ level in the mitochondrial matrix, whereas that of the extramitochondiral fraction became less affected. All the observed effects were dependent on the citrinin concentration.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Cell Biochemistry and Function 16 (1998), S. 173-181 
    ISSN: 0263-6484
    Keywords: AZT ; mitochondrial disease ; bioenergetics ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The possibility of tissue-specific effects regarding mitochondrial sensitivity to AZT was evaluated in this study. When mitochondria isolated from liver, kidney, skeletal and cardiac muscle were oxidizing glutamate, a dose-dependent inhibition by AZT of state 3 respiration was observed; using succinate as substrate the inhibition occurred only in skeletal and cardiac muscle mitochondria. The same results were obtained with FCCP-uncoupled mitochondria. NADH oxidase of intact and disrupted mitochondria, isolated from all four tissues was strongly inhibited. Succinate oxidase activity was inhibited by AZT only in intact mitochondria from skeletal and cardiac muscles, suggesting the involvement of succinate transport systems. Similarly, inhibition by the drug of the hydrolytic activity of H+-ATPase was observed only in mitochondria of these tissues. These effects taken together, indicate a tissue/carrier-specific inhibition in vitro, although its precise mechanism requires further research. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 7 Ill.
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