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  • 1
    Electronic Resource
    Electronic Resource
    Fabrication of PbS nanoparticles embedded in a polymer Film by a gas-aerosol reactive electrostatic deposition techniqueOVS acknowledges support from the Science and Engineering Research Council (SERC) of the UK, contract number GR/HO4466 and PJH is supported by a SERC studentship. (1994)
    Weinheim : Wiley-Blackwell
    Advanced Materials 6 (1994), S. 772-775 
    Details
    ISSN: 0935-9648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/adma.19940061013
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  • 2
    Electronic Resource
    Electronic Resource
    Polymerization of ethylene using a high-activity Ziegler-Natta catalyst. II. Molecular weight regulation (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 219-225 
    Details
    ISSN: 0887-624X
    Keywords: polymerization ; molecular weight ; ethylene ; Ziegler-Natta ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article describes studies on the variables that regulate the molecular weight in ethylene polymerization using a highly active Ziegler-Natta catalyst with hydrogen for molecular weight control. The dependence of the degree of polymerization on the concentration of catalyst, cocatalyst, monomer, partial pressure of hydrogen, and temperature has been established. The rate constant for chain transfer with cocatalyst has been evaluated. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080310126
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  • 3
    Electronic Resource
    Electronic Resource
    Polymerization of ethylene using a high-activity Ziegler-Natta catalyst. I. Kinetic studies (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 209-218 
    Details
    ISSN: 0887-624X
    Keywords: polymerization ; Ziegler-Natta ; catalysis ; ethylene ; kinetic ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Factors affecting the particular shape of kinetic rate-time profiles in the polymerization of ethylene with a MgCl2-supported TiCl4 catalyst activated by Al(C2H5)3 have been investigated. Examination of the dependence of the polymerization rate on the concentration of Al(C2H5)3 resulted in a Langmuir-Hinshelwood rate law. Analysis of the polymerization rate as a function of the polymerization temperature gave about 46 kJ mol-1 for the overall activation energy. Examination of the rapid decay of the polymerization rate with time showed that this decay is represented better by a first-order decay law than by a second-order one. © 1993 John Wiley & Sons, Inc.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080310125
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  • 4
    Electronic Resource
    Electronic Resource
    Tutorial to robust statistics (1991)
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 1-20 
    Details
    ISSN: 0886-9383
    Keywords: Averaging ; Median ; Outliers ; Regression ; Residuals ; Robustness ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this tutorial we first illustrate the effect of outliers on classical statistics such as the sample average. This motivates the use of robust techniques. For univariate data the sample median is a robust estimator of location, and the dispersion can also be estimated robustly. The resulting ‘z-scores’ are well suited to detect outliers. The sample median can be generalized to very large data sets, which is useful for robust ‘averaging’ of curves or images. For multivariate data a robust regression procedure is described. Its standardized residuals allow us to identify the outliers. Finally, a survey of related approaches is given. (This review overlaps with earlier work by the same author, which appeared elsewhere.)
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cem.1180050103
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  • 5
    Electronic Resource
    Electronic Resource
    Silanes on magnesium chloride studied by solid-state 29Si-NMR spectroscopy (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 2835-2838 
    Details
    ISSN: 0887-624X
    Keywords: NMR ; MAS ; silanes ; Ziegler-Natta ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 29Si cross-polarisation NMR was used to study the interaction between silanes and MgCl2 when co-milled. Large changes are seen for the 29Si chemical shift of the silane between the silane in solution and in the solid complex. Interpretation of the differences in chemical shift are hindered by the absence of an adequate semi-empirical theory. The 29Si chemical shift tensors confirm a strong interaction between the silane and MgCl2. © 1993 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080311121
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  • 6
    Electronic Resource
    Electronic Resource
    Glycine/Glycolic acid based copolymers (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1063-1069 
    Details
    ISSN: 0887-624X
    Keywords: biodegradable polymers ; glycine ; glycolic acid ; morpholine-2,5-dione ; glycolide ; ring-opening polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Glycine/glycolic acid based biodegradable copolymers have been prepared by ring-opening homopolymerization of morpholine-2,5-dione, and ring-opening copolymerization of morpholine-2,5-dione and glycolide. The homopolymerization of morpholine-2,5-dione was carried out in the melt at 200°C for 3 min using stannous octoate as an initiator, and continued at lower reaction temperatures (100-160°C) for 2-48 h. The highest yields (60%) and intrinsic viscosities ([η] = 0.50 dL/g; DMSO, 25°C) were obtained after 3 min reaction at 200°C and 17 h at 130°C using a molar ratio of monomer and initiator of 1000. The polymer prepared by homopolymerization of morpholine-2,5-dione was composed of alternating glycine and glycolic acid residues, and had a glass transition temperature of 67°C and a melting temperature of 199°C. Random copolymers of glycine and glycolic acid were synthesized by copolymerization of morpholine-2,5-dione and glycolide in the melt at 200°C, followed by 17 h reaction at 130°C using stannous octoate as an initiator. The morphology of the copolymers varied from semi-crystalline to amorphous, depending on the mole fraction of glycolic acid residues incorporated. © 1994 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080320608
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  • 7
    Electronic Resource
    Electronic Resource
    Iridium complexes of dehydroamino acids: The kinetic resolution of racemic diphosphines and their application in catalytic asymmetric hydrogenation (1991)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 345-354 
    Details
    ISSN: 0899-0042
    Keywords: iridium ; asymmetric hydrogenation ; dehydroamino acid esters ; enamide complexes ; resolution ; homogeneous catalysis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of chiral diphosphines with a configurationally pure cationic bis-enamide complex of iridium, bis(menthyl (Z)-α-benzamidocinnamate)-iridium tetrafluoroborate, is described. When the reactant ligand is racemic then kinetic resolution occurs with high specificity under the appropriate conditions. Since the iridium diphosphine complex is catalytically inactive in homogeneous hydrogenation, the residual enantiomer may be reacted with bis(norbornadiene)-rhodium tetrafluoroborate to produce an active catalyst. This effects the hydrogenation of methyl (Z)-α-acetamidocinnamate in optical yields comparable with those obtained separately with the enantiomerically pure ligand rhodium complex. The reaction of pure (+)- or (-)-enantiomer of bis(menthyl (Z)-α-benzamidocinnamate)-iridium tetrafluoroborate with enantiomerically pure diphosphines has been studied. Invariably one hand of the diphosphine reacts rapidly with a given enantiomer of the iridium complex to give a stable diphosphine iridium enamide complex in which the original configuration of the coordinated olefin is maintained. The other combination of enantiomers reacts much more slowly, in keeping with the kinetic resolution work, and produces an enamide complex which is unstable in solution, isomerising to a second diastereomer. Since the absolute configuration of the iridium bis-enamide complex has been established by X-ray crystallography, this experiment affords a method of determining the configuration of rhodium enamide complexes in asymmetric hydrogenation (assuming structural homology between Rh and Ir). In all cases the disfavoured enamide complex was the one involved in the catalytic pathway.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530030421
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  • 8
    Electronic Resource
    Electronic Resource
    Marked enantioselective protein binding in humans of ketorolac in vitro: Elucidation of enantiomer unbound fractions following facile synthesis and direct chiral hplc resolution of tritium-labelled ketorolac (1994)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 6 (1994), S. 642-648 
    Details
    ISSN: 0899-0042
    Keywords: ketorolac ; nonsteroidal antiinflammatory drugs ; chiral drugs ; enantiomers ; protein binding ; human serum albumin ; enantioselectivity ; pharmacokinetics ; fatty acids ; oleic acid ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The protein binding of the enantiomers of the nonopiate analgesic, ketorolac, was investigated in vitro using human plasma and solutions of human serum albumin (HSA) at physiological pH and temperature. In order to detect the very low levels of unbound enantiomers in protein solutions, tritium-labelled rac-ketorolac was synthesised by regiospecific isotopic exchange of the parent drug with tritiated water as the isotope donor. Radio-chemical purification of this compound by reversed-phase HPLC followed by direct resolution using a chiral α1-acid glycoprotein (Chiral-AGP) HPLC column afforded labelled enantiomers of high specific activity. The in vitro use of (R)- and (S)-[3H4]ketorolac enabled reproducible radiometric detection of enantiomers in protein solution ultrafiltrate. The unbound fractions of (R)- and (S)-ketorolac [fu(R) and fu(S), respectively] were determined when drug was added to various plasma or albumin solutions as either the separate enantiomers or as the racemate. Over an enantiomeric plasma concentration range of 2.0 - 15.0 μg/ml, fu(S) (mean range: 1.572 - 1.795%) was more than 2-fold greater (P 〈 0.001) than fu(R) (mean range: 0.565 - 0.674%). Both fu(R) and fu(S) were constant over this concentration range, and each was unaffected by the presence of the corresponding antipode (P 〉 0.05). At a concentration of 2.0 μg/ml in 40.0 g/liter fatty acid-free HSA, fu(R) and fu(S) were approximately 0.5 and 1.1%, respectively, and both values declined with increasing concentrations of the long chain fatty acid, oleic acid. We have previously shown that the pharmacokinetics of ketorolac in humans are markedly enantioselective and suggest in this report that these differences are largely the result of substantial differences in the protein binding of ketorolac enantiomers. These findings stress the importance of monitoring the unbound concentrations of the enantiomers of chiral drugs if correct interpretations are to be made of enantioselective pharmacokinetic data. © 1994 Wiley-Liss, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530060807
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  • 9
    Electronic Resource
    Electronic Resource
    Enantioselective pharmacodynamics of the nonsteroidal antiinflammatory drug ketoprofen: In vitro inhibition of human platelet cyclooxygenase activity (1992)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 4 (1992), S. 484-487 
    Details
    ISSN: 0899-0042
    Keywords: ketoprofen enantiomers ; thromboxane ; in vitro activity ; 2-arylpropanoic acids ; sigmoidal Emax modelling ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pharmacological activity of ketoprofen enantiomers was investigated in humans by an in vitro method. The antiplatelet effect of ketoprofen was assessed by measuring the inhibition of platelet thromboxane B2 (TXB2) generation during the controlled clotting of whole blood obtained from each of four healthy volunteers. Ketoprofen was added separately to whole blood as a range of concentrations of (1) predominantly (S)-ketoprofen, (2) racemic ketoprofen, and (3) predominantly (R)-ketoprofen. (S)-Ketoprofen was found to be solely active at inhibiting human platelet TXB2 production; (R)-ketoprofen was devoid of such activity and did not modify the potency of its optical antipode. A relationship between the percentage inhibition of TXB2 generation and the unbound concentration of (S)-ketoprofen in serum was modelled according to a sigmoidal Emax equation. The mean (±SD) serum unbound concentration of (S)-ketoprofen required to inhibit platelet TXB2 generation by 50% (EC50) was 0.320 (±0.062) ng/ml. This value for ketoprofen is considerably lower than previously reported values for (S)-ibuprofen and (S)-naproxen. © 1992 Wiley-Liss, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530040805
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  • 10
    Electronic Resource
    Electronic Resource
    Stereoselective analysis of ketorolac in human plasma by high-performance liquid chromatography (1993)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 5 (1993), S. 31-35 
    Details
    ISSN: 0899-0042
    Keywords: ketorolac enantiomers ; HPLC ; plasma concentrations ; nonnarcotic analgesic ; nonopiate analgesic ; diastereomers ; nonsteroidal antiinflammatory drugs (NSAIDs) ; stereoselective pharmacokinetics ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A high-performance liquid chromatographic (HPLC) analytical method is described for the quantification of the (R)- and (S)-enantiomers of ketorolac when present together in human plasma. The method involves derivatization with thionyl chloride/(S)-1-phenylethylamine and subsequent reversed-phase chromatography of the diastereomeric (S)-1-phenylethylamides of (R)- and (S)-ketorolac. The method is suitable for the analysis of large numbers of plasma samples and has been applied in this report to a pharmacokinetic study of ketorolac enantiomers upon intramuscular administration of racemic drug to a human subject. The limit of quantification for each enantiomer of ketorolac is 50 ng/ml (signal-to-noise ratio 〉 10). © 1993 Wiley-Liss, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530050107
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