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Date of Award
Dissertation - Pacific Access Restricted
Doctor of Philosophy (Ph.D.)
Michael J. Minch
First Committee Member
Donald K. Wedegaertner
Second Committee Member
Paul A. Richmond
Third Committee Member
Richard P. Dodge
Fourth Committee Member
Paul A. Gross
Fifth Committee Member
Charles A. Matuszak
The proton and carbon-13 NMR spectra of N1Acetyl- and N8Acetylspermidine in D20 were completely assigned by a variety of double resonance and two dimensional methods. The pH dependence of carbon chemical shifts were analyzed by a regression method to estimate the acid dissociation constants for the first and second protonations of both acetylspermidines. N1Acetylspermidine is both less acidic for the first protonation and more acidic for the second protonation. These effects can be explained in terms of the influence of intervening methylene groups on the acidity of the ammonium nitrogens. Natural abundance carbon-13 spin lattice relaxation times (T1-values) of both acetylspermidines were determined as a function of amine concentration (25 mM to 178 mM) in the presence of 75 mM bp calf thymus DNA. Binding to DNA immobilized either polyamine with the most pronounced effect observed for the more internal methylene carbons. Spin lattice relaxation studies of [13CH3] labeled acetylspermidines permitted estimates of binding constants for 0.5 mM to 10 mM polyamine with 3.3 mM bp calf thymus DNA. Under these conditions N8Acetylspermidine binds DNA less tightly than N1Acetylspermidine, suggesting that the role of chromatin associated spermidine acetylation may be to reduce spermidine binding to DNA.
Ma, Yong. (1989). Interactions of N-Acetylspermidines with DNA. University of the Pacific, Dissertation - Pacific Access Restricted. https://scholarlycommons.pacific.edu/uop_etds/3048
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