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    Adenosine 5’-triphosphate: Dephosphorylation promoted by Co(III) complexes and metal ion/polyamine systems

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    Issue Date
    1986-05-31
    Author
    Yohannes, Paulos G.
    Publisher
    University of Kansas
    Type
    Dissertation
    Degree Level
    Ph.D.
    Discipline
    Chemistry
    Rights
    This item is protected by copyright and unless otherwise specified the copyright of this dissertation is held by the author.
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    Abstract
    Three model systems for the metal ion-dependent enzymatic hydrolysis of ATP have been examined.

    The metal ion/ATP system, La('3+)/ATP, was examined at pH 7.6 and 13. Rapid hydrolysis and formation of pyrophosphate was observed at pH 13. The rate enhancement was by a factor of about 300. At pH 7.6, however, a slower rate of hydrolysis of ATP was noted in the presence of La('3+).

    The Co('3+) complex/ATP system was used to form substitution inert Co('3+)-ATP complexes. From ('31)P NMR and HPLC studies, various mixtures of isomers are believed to exist in solution. The dephosphorylation of ATP promoted by the Co('3+) complexes has pointed to the importance of formation of a dinuclear Co('3+)-ATP complex and/or coordinated hydroxide for rate enhancement.

    The third model system examined resembled its biological counterpart, M('2+)/enzyme/ATP. The model system, M('n+)/polyamine/ATP, was compared with M('n+)/ATP and polyamine/ATP systems. The twenty four-membered ring macrocycle 1,4,7,13,16,19-hexaaza-10,22-dioxocyclotetracosane, which is the most efficient among the polyamines examined in dephosphorylating ATP, was used in the presence of various metal ions (Zn('2+), Cd('2+), La('3+), Mg('2+), Ca('2+)) to investigate the dephosphorylation and complexation of ATP at pH 7.6. A phosphoramidate intermediate was observed only for this polyamine and has proven the reaction to be under strict structural control. The importance of certain metal ions (Ca('2+), Mg('2+) and La('3+)) both in the synthesis of pyrophosphate from the reaction of the phosphoramidate and inorganic phosphate (phosphorylation) and in the dephosphorylation of ATP in the presence of a polyammonium macrocycle was demonstrated. The dephosphorylation of ATP was enhanced by a factor of about 845 in the presence of La('3+) and 24 -N(,6)O(,2). The ternary complexes, M('n+)/ 24 -N(,6)O(,2)/ATP, were examined using ('31)P and ('13)C NMR techniques.
    Description
    Dissertation (Ph.D.)--University of Kansas, Chemistry, 1986.
    URI
    http://hdl.handle.net/1808/32539
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    • Dissertations [4660]

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    KU Libraries
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    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

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