The kinetics and mechanism of hydrolysis of both activated and unactivated phosphate diesters in the presence of aqueous solutions of Ce(III) salts are studied in detail. In the presence of 20 mM Ce$ rm (ClO sb4) sb3 (pH 8, 37 sp circ C)$ a DNA dinucleotide (dApdA) is converted to the nucleoside (dA) and inorganic phosphate with a half-life of approximately 100 minutes. This reaction is oxygen dependent and a mechanism involving the activation of oxygen by Ce(III) to give a Ce(IV) coordinated peroxide dianion as the active species is proposed. / The addition of 20 mM hydrogen peroxide to 2mM La(III) (pH 7.0, 25$ sp circ$C) results in a 34,000 fold increase in the rate of BNPP hydrolysis over that observed in the presence of 2mM La(III) alone and an overall 5 x l0$ sp8$ fold rate increase over the uncatalyzed rate. Incorporation of $ sp{18}$O from hydrogen peroxide into the inorganic phosphate product and evidence from the reaction kinetics and potentiometric titrations indicate that the mechanism involves nucleophilic attack of a La(III) coordinated peroxide dianion upon the substrate. / La(III) hydroxide clusters formed from the combination of La(III) (20 mM) and NaOM (40 mM) rapidly converts an RNA dinucleotide (ApA) to the monophosphates (2$ sp prime$-AMP and 3$ sp prime$-AMP) (t$ sb{1/2}$ = 8 sec at pH 8.7, 20$ sp circ$C). The presence of molecular oxygen does not improve the efficiency of Ce(III) in cleaving ApA; however, it does assist in the cleavage of the monophosphates which are not cleaved by Ce(III) in the absence of O$ sb2$ or La(III).
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.28535 |
| Date | January 1994 |
| Creators | Takasaki, Bryan K. |
| Contributors | Chin, Jik (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001425052, proquestno: NN00137, Theses scanned by UMI/ProQuest. |
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