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  • ab initio calculations  (1)
  • anaerobic  (1)
  • Wiley-Blackwell  (2)
  • American Chemical Society
  • Annual Reviews
  • Blackwell Science Ltd
  • Institute of Physics
  • Wiley
  • 2010-2014
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  • Wiley-Blackwell  (2)
  • American Chemical Society
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  • Blackwell Science Ltd
  • Institute of Physics
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  • 2010-2014
  • 1995-1999  (2)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 869-876 
    ISSN: 0947-6539
    Keywords: ab initio calculations ; silaguanidinium cations ; silylium cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantium mechanical calculations at the MP2/6-31 G(d) level are reported for the silaguanidinium cation Si(NH2)3+ (1) and derivatives thereof. The equilibrium structure 1a has D3 symmetry with planar amino groups rotated out of the SiN3 plane by 19.60. The Si-N bond length of 1 a (1.658 Å) is intermediate between a single and a double bond. Isodesmic reactions show that the stabilization of the silylium cation 1 a by the amino groups (63.5 kcal mol-1) is about 40% of the resonance stabilization of the guanidinium cation (159.3 kcal mol-1), but 1 a is clearly better stabilized than alkyl-substituted silylium cations. The electronic stabilization of 1 a by the amino groups is also made obvious by the calculated complexation energy with one molecule of water. The calculated stabilization through complexation of water at HF/6- 31 G(d) is markedly lower for Si(NH2)3-(H2O)+ (6) (28.8 kcal mol-1) than for SiMe3(H2O)+ (40.6 kcal mol-1). The tris(dimethylamino) silylium cation Si(N-Me2)3+ (8) is even more stable than 1 a. The complexation energy of Si(NMe2)3-(H2O)+ (10) is only 17.3 kcal mol-1. IGLO calculations of the 29Si N M R chemical shifts predict that 1 a and 8 should not show the same extremely low shielding that is calculated for alkyl-sub-stituted silylium ions. The calculated 29Si resonances for 8 are in reasonable agreement with the experimental N M R spectrum of (Me2N)3 SiB(C6F5)4. AM 1 calculations predict that the substituted tripyrrolidino silylium cation 12 would be an even better candidate for a stable tricoordinate silylium cation in condensed phases. One of the pyrrolidine rings of 12 has tert-butyl groups in the 2 and 5 positions, which serve as a steric fence around the silicon atom.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 59 (1998), S. 732-746 
    ISSN: 0006-3592
    Keywords: Desulfovibrio vulgaris ; hydrogen cycling ; kinetics ; thermodynamics ; modeling ; anaerobic ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A unified model for the growth of Desulfovibrio vulgaris under different environmental conditions is presented. The model assumes the existence of two electron transport mechanisms functioning simultaneously. One mechanism results in the evolution and consumption of hydrogen, as in the hydrogen-cycling model. The second mechanism assumes a direct transport of electrons from the donor to the acceptor, without the participation of H2. A combination of kinetic and thermodynamic conditions control the flow of electrons through each pathway. The model was calibrated using batch experiments with D. vulgaris grown on lactate, in the presence and absence of sulfate, and was verified using additional batch experiments under different conditions. The model captured the general trends of consumption of substrates and accumulation of products, including the transient accumulation and consumption of H2. Furthermore, the model estimated that 48% of the electrons transported from lactate to sulfate involved H2 production, indicating that hydrogen cycling is a fundamental process in D. vulgaris. The presence of simultaneous electron transport mechanisms might provide D. vulgaris with important ecological advantages, because it facilitates a rapid response to changes in environmental conditions. This model increases our ability to study the microbial ecology of anaerobic environments and the role of Desulfovibrio species in a variety of environments. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 59:732-746, 1998.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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