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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0365-9496
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The growth-regulating factor MDGI belongs to the fatty acid binding proteins of which the amino acid sequence is known. Starting from hydrodynamic and dichroic measurements which yield estimations about mass, diameter, thickness, and content of α and β structure of the MDGI protein, we used theoretical methods to calculate the structures and electrostatic properties of selected β-chain sequences. The hydrophobic character of possible binding sites for fatty acids is demonstrated by the molecular electrostatic potential and field of this structures. A nonstandard turn element, formed by an H-bridge between polar side chains, Lys-Leu-Gly-Val-Glu, which connects two extended β chains, was found. Bound oleic acid could be able to stabilize such turn structure, which seems to appear also at the entrance of the cavity of two other proteins. The optimization of an oleic acid-turn van der Waals complex results in an interaction energy of about -50 kJ/mol originating mainly from the dispersion term and shows the participation of the four hydrophobic side chains Phe 64, Leu 66, Val 68, and Phe 70. Of these, at least Phe 64 and Phe 70 are known as possible binding sites of fatty acids.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Novel Cluster Frameworks from the Reactions of the Unsaturated Clusters Fe4(CO)11(μ4-PR)2 with AlkynesThe unsaturated clusters Fe4(CO)11(μ4-PR)2 (1-3, R = Ph, p-Tol, t-Bu) react with terminal alkynes primarily by insertion of the alkyne between one phosphorus and two iron atoms. The structure analysis of Fe4(CO)11(μ4-PTol)[μ4-P(Tol)-CMeCH] and NMR studies in solution show that the insertion products exist as two isomers, which differ by the orientation of the alkyne (P—CR—CH—Fe/P—CH—CR—Fe), and whose interconversion in solution can be catalyzed by bases. Starting from 3, additionally and preferentially alkyne-containing clusters are formed with CO elimination, which contain a novel Fe4P2C2 framework that can be derived from a pentagonal bipyramid with an equatorial Fe2PC2 unit as evidenced by the structure determination of Fe4(CO)9(μ3-P-tBu)[μ4-P-(tBu)CHCMe]. The primary alkyne-insertion products are easily induced by an excess of donor ligands [CO, P(OM)3, tBuNC] or by iodine oxidation to eliminate one ironcarbonyl unit and form the clusters Fe4(CO)9(μ3-P-tBu)[μ4-P-(tBu)CHCMe] and substituted derivatives thereof. For these the structure analysis of the (PhPCHCMePPh) compound proves the PCCP sequence and a side-on coordination of the C2 unit to one iron atom. The degradation with P(OMe)3 and tBuNC produces as intermediates the substitution derivatives Fe4(CO)10L(μ4-PPh)-[μ4-P(Ph)CRCH], which also exist as two isomers with different orientation of the CR—CH unit.
    Notes: Die ungesättigten Cluster Fe4(CO)11(μ4-PR)2 (1-3, R = Ph, p-Tol, t-Bu) reagieren mit terminalen Alkinen primär unter Insertion des Alkins zwischen einem Phosphor- und zwei Eisen-Atomen. Die Strukturanalyse von Fe4(CO)11(μ4-PTol)[μ4-P(Tol)-CMeCH] und NMR-Studien in Lösung zeigen, daß die Insertionsprodukte in Form von zwei Isomeren vorliegen, die sich durch die Orientierung des Alkins (P—CR—CH—Fe/P—CH—CR—Fe) unterscheiden und deren gegenseitige Umwandlung in Lösung sich durch Basen katalysieren läßt. Aus 3 entstehen zusätzlich und bevorzugt unter CO-Abspaltung alkinhaltige Cluster mit einem neuartigen Fe4P2C2-Gerüst, das sich von einer pentagonalen Bipyramide mit äquatorialer Fe2PC2-Einheit ableiten läßt, wie die Strukturanalyse von Fe4(CO)9(μ3-P-tBu)[μ4-P-(tBu)CHCMe] belegt. Die primären Alkin-Insertionsprodukte werden durch überschüssige Donorliganden [CO, P(OM)3, tBuNC] und durch Oxidation mit Iod leicht unter Abspaltung einer Eisencarbonyl-Einheit zu den Clustern Fe3(CO)9[μ3-μ3-P(R)-CHCR′PR] bzw. substituierten Derivaten davon abgebaut. Für diese beweist die Strukturanalyse der (PhPCHCMePPh)-Verbindung die PCCP-Verknüpfung und eine Seitwärtskoordination der C2-Einheit an ein Eisen-Atom. Der Abbau verläft mit P(OM)3 und tBuNC über die Substitutionsprodukte Fe4(CO)10L(μ4—PPh)-[μ-P(Ph)CRCH], die ebenfalls in Form von zwei Isomeren mit unterschiedlicher CR—CH-Orientierung vorkommen.
    Additional Material: 3 Ill.
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