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  • 1
    Electronic Resource
    Electronic Resource
    Thermodynamics of mucopolysaccharide-dye binding. I. Identification of free and bound dye via membrane filtration: Acridine orange-dermatan sulfate system (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 685-693 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stoichiometric mixtures of acridine orange with dermatan sulfate at total dye concentrations ≤ 1 × 10-5 M show fluorescence maxima at 540 nm and 660 nm on excitation at 436 nm. By means of membrane filtration, it is directly demonstrated that the species emitting at 540 nm is due only to unbound dye whereas the 660-nm emitting species is due to bound dye. It is, therefore, possible to differentiate unbound acridine orange from its dermatan sulfate complex solely by spectroscopic methods. Thermodynamic binding parameters can be calculated from rapid spectroscopic measurements without disturbing the system.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1977.360160316
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  • 2
    Electronic Resource
    Electronic Resource
    Thermodynamics of mucopolysaccharide-dye binding. II. Binding constant and cooperativity parameters of acridine orange-dermatan sulfate system (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 695-702 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the acridine orange-dermatan sulfate system, free and bound dye can be distinguished from each other spectroscopically. This permits the use of fluorometric methods to study the binding of acridine orange to the acid mucopolysaccharide dermatan sulfate. Experiments were conducted at 24°C in 10-3 M citrate/phosphate buffer at pH = 7.0. The binding of the dye is highly cooperative, as evidenced by considerable interaction between adjacent bound dye molecules. Analysis of the data indicates that dermatan sulfate binds 2.3 ± 0.3 mol of acridine orange per dermatan sulfate uronic acid residue with a cooperative binding constant, Kq ranging from 4.9 to 6.0 × 105 M-1 which corresponds to a free energy of 7.74 ≤ ΔG° ≤ 7.86. The cooperativity parameter q apparently increases with increasing polymer-to-dye ratio.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1977.360160317
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  • 3
    Electronic Resource
    Electronic Resource
    Thermodynamics of mucopolysaccharide-dye binding. III. Thermodynamic and cooperativity parameters of acridine orange-heparin system (1979)
    New York : Wiley-Blackwell
    Biopolymers 18 (1979), S. 493-505 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Binding isotherms for acridine orange (AO)-heparin systems can be evaluated solely on the basis of quantitative fluorescence spectroscopic measurements. The evaluation of thermodynamic parameters indicates that the interactions of AO with heparins from several animal sources are similar to each other in magnitude. Binding is highly exothermic (ΔH = -6 kcal mol-1) and is stabilized by dye-polymer and dye-dye (coopertive) interactions, as well as by entropic factors (ΔS = +7 e.u.). The predominant stabilizing factor appears to be the electrostatic attraction between the AO cation and the heparin polyanion, although the other factors are important as well. At 24°C the value of the cooperative binding constants for the various heparins range from 8.8 to 11.3 × 105M-1, corresponding to a free energy of -8 kcal mol-1. The degree of cooperativity, which is a direct measure of dye-dye interaction, varies with polymer:dye ratio; the theoretical basis for this variation remains to be elucidated. Electrophoretic data indicate that each heparin sample consists of a mixture of species, each with its own charge density. This precludes definitive interpretation of observed small differences in the values of the thermodynamic parameters among the various samples until each sample can be resolved into its components.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1979.360180302
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  • 4
    Electronic Resource
    Electronic Resource
    The effect of surface modification of aluminium hydroxide on the crystallisation behaviour of aluminium hydroxide filled polypropylenes (1996)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 235 (1996), S. 193-203 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Diese Studie umfaßt Verbundwerkstoffe auf Polypropylen(PP)-Basis (Homopolymeres und schlagzäh modifiziertes Copolymeres) und oberflächenaktiviertes Aluminiumhydroxid. Differentialkalometrische Untersuchungen (DSC) und Röntgenbeugungsanalysen (XRD) wurden vorgenommen. Die verwendeten Aktivierungsmittel umfaßten ein 2-Dodecen-1-yl-bernsteinsäureanhydrid (DDSA) als Dispergiermittel und ein kommerzielles Haftmittel auf Silan-Basis (BA Chemicals S21). Das mit DDSA behandelte Al(OH)3 zeigte eine wesentlich geringere Abhängigkeit der Keimbildung vom Füllstoffgehalt und in einigen Verbunden ein verstärktes Wachstum von β-PP. Bei Aktivierung durch S21 war die Wirkung des Füllstoffs als Nukleierungsmittel nicht aufgehoben, auch wenn die Elastomerphase im Falle des schlagzäh modifizierten PP den Füllstoff einbettet. Untersuchungen mittels DSC und XRD wiesen darauf hin, daß bei unbehandeltem Füllstoff ein direkter Zusammenhang zwischen Keimbildung und Füllstoffoberfläche besteht. Bei mit S21 behandeltem Füllstoff war dies jedoch nicht der Fall; die keimbildung war vom Zufall und/oder von den Fließbedingungen bestimmt, nicht von der Füllstoffoberfläche.
    Notes: Composites based on polypropylene (PP) (homopolymer and impact modified copolymer) and surface modified aluminium hydroxide (Al(OH)3) have been studied using differential scanning calorimetry (DSC) and X-ray diffraction (XRD). Filler surface modifiers used included 2-dodecen-1-yl succinic anhydride (DDSA) as a dispersant and a commercial silane based coupling agent system (BA Chemicals S21). Treatment of the Al(OH)3 with DDSA led to a considerable reduction of the capacity of the filler to nucleate crystallisation in the PP and, in some composites, promoted growth of β-PP. With the S21 treatment, however, a nucleation effect was still apparent, despite encapsulation of the filler particles with the elastomeric phase in the case of the impact modified PP. DSC and XRD studies indicated that with the untreated filler nucleation was directly associated with the filler surface. However, with the S21 treated filler this was not the case and PP nucleation was random and/or flow induced with no association with the filler surface.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1996.052350116
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  • 5
    Electronic Resource
    Electronic Resource
    Thermodynamics of the partition of chondroitin sulfate-hexadecylpyridinium complexes in butanol/aqueous salt biphasic solutions (1978)
    New York : Wiley-Blackwell
    Biopolymers 17 (1978), S. 2601-2608 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermodynamics of the partition of chondroitin sulfate-hexadecylpyridinium complexes wee studied in order to gain further insight into the mechanisms responsible for the sensitivity of the relative solubility of these complexes in aqueous slat and butanol phases to small changes in slat concentration. The dependence of the partition coefficient was measured as a function of temperature at three different salt concentrations. Increasing the temperature was found to favor the form of the complex which was soluble n the aqueous phase. Although the transition could be induced by temperature changes, he transition occurred over a 20°C range in temperature. The transition from the aqueous phase to the butanol phase was strongly exothermic, with ΔH = -22.3 kcal/mol polymer. The value of ΔS was found to be dependent on the salt concentration, ranging from -72.7 e.u./mol polymer in 0.05125M NaCl to -77.1 e.u./mol polymer in 0.05375M MaCl. When placed on a disaccharide basis, the corresponding values are ΔH = -402 cal/mol and ΔS = -1.31 to -1.3 e.u./mol. The sharpness of he transition was found to be due t the similarity in magnitude of ΔH and TΔS, and on the dependence of the later upon the salt concentration.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1978.360171108
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  • 6
    Electronic Resource
    Electronic Resource
    Asymmetric synthesis of tertiary alcohols from α-halo boronic esters (1990)
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 1 (1990), S. 65-74 
    Details
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of pinanediol boronates with (1,1-dichloroethyl)lithium generated in situ at -78°C followed by rearrangement of the resulting borate complex 2S in the presence of zinc chloride at 25°C has resulted in chirally biased insertion of the 1-chloroethyl group into the carbon-boron bond. (s)-Pinanediol phenylboronate (7) produced (s)-pinanediol (1S)-(1-chloro-1-phenylethyl)boronate (8S) in 92% DE. Nonstererospecific reaction with ethylmagnesium bromide to form (s)-pinanediol (1S)-(1-phenyl-1-methylpropyl)boronate (5S) reduced the DE to 88%. Peroxidic deboronation yielded (R)-(+)-2-phenyl-2-butanol (6R) (84% EE). (s)-Pinanediol ethylboronate (4) with (1,1-dichloroethyl)lithium showed the opposite chiral preference, yielding (s)-pinanediol (1R)-(1-chloro-1-methylpropyl)boronate (3R) (89% DE), which was converted by phenylmagnesium bromide followed by hydrogen peroxide to 6R (76% EE). Diastereoselections were small in reactions of (1,1-dichloroethyl)-lithium with n-alkylboronates 9a and 13 and with cyclohexylboronate 9c. The 13 was converted to the enantiomer of the insect pheromone frontalin (17) (21% EE). Good diastereoselections were found with α-substituted alkylboronates 9b and 18, but the configurations of the products could not be determined. (s)-Pinanediol (1,1-dichloroethyl)boronate (1) reacts with Grignard reagents via an intermediate borate 2R with negligible diastereoselection.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hc.520010110
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  • 7
    Electronic Resource
    Electronic Resource
    Measurement of ethyl carbamate in blood by capillary gas chromatography/mass spectrometry using selected ion monitoring (1990)
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 19 (1990), S. 27-31 
    Details
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methodology is presented for convenient, reproducible and direct measurement of blood concentrations of ethyl carbamate, an experimental animal carcinogen. Extraction techniques requiring 20 μl of blood and selected ion monitoring using ethyl (13C, 15N)carbamate as internal standard enabled quantification of ethyl carbamate concentrations ranging from 50 ng ml-1 to 100 m̈g ml-1. Coefficients of variation at several representative concentrations averaged less than 4%. The method was used to determine the time course of elimination of ethyl carbamate from mice receiving doses of 125 m̈mol kg-1.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bms.1200190104
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  • 8
    Electronic Resource
    Electronic Resource
    The characteristics of polydienes obtained with lanthanide-based catalysts (1996)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 47 (1996), S. 450-454 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyisoprene and polybutadiene samples, prepared from the respective monomers using lanthanide-based catalysts, have been analyzed in terms of microstructure, glass transition temperatures and stabilities to thermo-oxidative degradation. Quantitative determination of 1,4-cis/trans, 1,2- and 3,4-contents have been made from the IR spectra of the polymers. Attempts to use 1H and 13C NMR and Raman spectroscopy to analyze the microstructure of the materials has at best proved only partially successful. TGA and IR spectroscopy have been used to study the influence of catalyst residue on the thermo-oxidative degradation of the polymers.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1996.010471005
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  • 9
    Electronic Resource
    Electronic Resource
    Ueber die bei Einwirkung von Schwefelwasserstoff auf ameisensaures Blei in der Hitze sich bildende Schwefelverbindung (1863)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 126 (1863), S. 67-71 
    Details
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.18631260107
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  • 10
    Electronic Resource
    Electronic Resource
    Triethylaluminum - titanium tetrachloride catalysts for preparation of crystalline polystyrene (1960)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 45 (1960), S. 195-204 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction between Et3Al and TiCl4 is discussed, with emphasis on the effect of temperature, concentration, stoichiometry, and order of component addition on the ability of products to catalyze the isotactic polymerization of styrene. A well-defined peak in relative catalyst activity becomes apparent when the interaction of these variables is followed by measuring the average oxidation state of titanium. Experimentally, the polymerization is first-order with respect to styrene and titanium, although efficiency of Ti use is small. The mode of polymerization is characterized by a lower activation energy for active site generation and a higher activation energy for termination than is typical of free-radical polymerization. A convenient procedure for laboratory preparation of isotactic polystyrene employing the Et3Al/TiCl4 catalyst is given.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1960.1204514520
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