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  • Articles: DFG German National Licenses  (2)
  • Antitumor agents  (1)
  • Cytochrome c  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1551-1555 
    ISSN: 0009-2940
    Keywords: Antitumor agents ; Nucleotides ; Palladium ; Hydrogen bonds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The compound [Pd(en)(5′-IMP-N7)2].11 H2O, where 5′-IMP = inosine 5′-monophosphate, crystallizes in the tetragonal space group P4322 with the unit cell parameters: a = b = 12.060(5) and c = 28.510(5) Å, V = 4147(3) Å3, Z = 4. A head-to-tail orientation with A configuration is observed for the nucleotides which are coordinated through the N(7) positions such that d[Pd-N(7)] = 2.053(8) Å. The sugar moieties exhibit anti orientations toward the purine bases while their pukkers adopt C(3)′-endo conformation. The overall conformation about the phosphate backbone is gauche+. Intramolecular hydrogen bonding is observed between the phosphates and the NH groups of the en ligand with a donor-acceptor distance of 2.88 Å. The coordination mode of the solid-state structure is shown to be identical to that observed by 1H-NMR spectroscopy in solution under slightly acidic conditions, where the N (l) positions of the nucleotides are protonated. The results are discussed in reference to closely related systems reported in the literature with emphasis on the importance of hydrogen bonding in such complexes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-1948
    Keywords: Cytochrome c ; Chromium(v) ; Saturation kinetics ; Separation of K and kET ; Volume profile ; Kinetics ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The irreversible outer-sphere electron-transfer reaction between trans-bis(2-ethyl-2-hydroxybutanoato(2-))oxochromate(v) and cytochrome cII was investigated as a function of pH, concentration, temperature and pressure. The plot of the observed pseudo-first order rate constant as a function of the CrV concentration shows a clear trend towards saturation at higher CrV concentrations, from which the precursor formation constant and the electron-transfer rate constant could be separated (K = 37 ± 5 M-1 and kET = 1510 ± 180 s-1 at pH 4.8 and 279 K). In the low CrV concentration range the second-order electron-transfer rate contants were measured as a function of temperature (ΔH# = 20.9 ± 0.6 kJ mol-1; ΔS# = -79.9 ± 2.1 J K-1 mol-1; ΔG# (279 K) = 43.2 kJ mol-1). High-pressure experiments were performed at two different pH values. The kinetic (stopped-flow) and thermodynamic (electrochemical) measurements as a function of pressure enabled the construction of a volume profile for the system at 279 K. The activation volumes for the redox process are -9.2 ± 0.2 (pH 5.0) and -11.1 ± 0.8 cm3 mol-1 (pH 4.7), and the overall reaction volumes were estimated to be -7 ± 2 (pH 5.0) and -10 ± 2 cm3 mol-1 (pH 4.7) . The transition state of the redox reaction lies to a large extent on the product side and can be described as “late”. The results are discussed in comparison to earlier measurements using cobalt and ruthenium complexes as reaction partners for cytochrome c.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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