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Date of Award

1989

Document Type

Dissertation - Pacific Access Restricted

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Graduate School

First Advisor

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

Abstract

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.

Pages

121

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