Library

feed icon rss

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
  • 1
    ISSN: 0948-5023
    Keywords: Keywords Human Carbonic Anhydrase II ; Semiempirical MO Theory ; AM1 ; Enzyme Catalysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The approach of CO2 to a series of active site model complexes of human carbonic anhydrase   II (HCAII) and its catalytic hydration to bicarbonate anion have been investigated using semiempirical MO theory (AM1). The results show that direct nucleophilic attack of zinc-bound hydroxide to the substrate carbon occurs in each model system. Further rearrangement of the bicarbonate complex thus formed via a rotation-like movement of the bicarbonate ligand can only be found in active site model systems that include at least one additional water molecule. Further refinement of the model complex by adding a methanol molecule to mimic Thr-199 makes this process almost activationless. The formation of the final bicarbonate complex by an internal (intramolecular) proton transfer is only possible in the simplest of all model systems, namely {[Im3Zn(OH)]+·CO2}. The energy of activation for this process, however, is 36.8 kcal·mol−1 and thus too high for enzymatic catalysis. Therefore, we conclude that within the limitations of the model systems presented and the level of theory employed, the overall mechanism for the formation of the bicarbonate complex comprises an initial direct nucleophilic attack of zinc-bound hydroxide to carbon dioxide followed by a rotation-like rearrangement of the bicarbonate ligand via a penta-coordinate Zn2+ transition state structure, including the participation of an extra active site water molecule.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 25 (1986), S. 673-682 
    ISSN: 0570-0833
    Keywords: Reaction dynamics ; Coordination modes ; High-pressure chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to understand the dynamics of chemical reactions in general, detailed information on electronic, structural and kinetic properties is required. The key questions on how chemical reactions actually occur can in many cases only be answered in terms of information obtained from kinetic studies. In conventional kinetic studies of chemical reactions in solution, the variables usually selected include concentration, acidity, solvent, and temperature. In recent years, pressure has become an additional selected variable in such studies. It enables the measurement of the volume of activation and the construction of reaction volume profiles and thus assists in the elucidation of the underlying mechanism; it also completes the comprehension of reaction kinetics by adding another kinetic parameter that the suggested reaction mechanism must account for. Furthermore, the volume of activation is the only transition state property that can be correlated with the corresponding ground state property in an experimentally simple manner. In this paper, the insights so gained in our understanding of the dynamics of reactions involving coordination complexes will be presented. Such reactions are of fundamental interest to chemists since they often form the basis of catalytic, biological, environmental and energy related processes. Any additional information that will add to the understanding of the reaction dynamics is therefore of exceptional importance.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...