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Biophys J, December 1999, p. 3242-3251, Vol. 77, No. 6
Department of Biochemistry, Molecular Biology, and Biophysics, University of Minnesota, St. Paul, Minnesota 55108 USA
In this paper we analyze published data on
H and
S values for the DNA melting
transition under various conditions. We show that there is a
significant heat capacity increase
Cp
associated with DNA melting, in the range of 40-100 cal/mol K per base
pair. This is larger than the transition entropy per base pair,
S0
25 cal/mol K. The ratio of
Cp/
S0 determines
the importance of heat capacity effects on melting. For DNA this ratio
is 2-4, larger than for many proteins. We discuss how
Cp values can be extracted from experimental
data on the dependence of
H and
S on the
melting temperature Tm. We consider studies of
DNA melting as a function of ionic strength and show that while
polyelectrolyte theory provides a good description of the dependence of
Tm on salt, electrostatics alone cannot explain the accompanying strong variation of
H and
S. While Tm is only weakly
affected by
Cp, its dependence on one
parameter (e.g., salt) as a function of another (e.g., DNA composition)
is determined by
Cp. We show how this
accounts for the stronger stabilization of AT relative to GC base pairs
with increasing ionic strength. We analyze the source of discrepancies
in
H as determined by calorimetry and van't Hoff
analysis and discuss ways of analyzing data that yield valid van't
Hoff
H. Finally, we define a standard state for DNA
melting, the temperature at which thermal contributions to
H and
S vanish, by analyzing experimental
data over a broad range of stabilities.
Biophys J, December 1999, p. 3242-3251, Vol. 77, No. 6
© 1999 by the Biophysical Society 0006-3495/99/12/3242/10 $2.00
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