Abstract
The goal of this chapter is to present a critical survey of spectroscopic and calorimetric methods for obtaining thermodynamic data on conformational transitions in oligonucleotides. A comprehensive compilation of the large body of published thermodynamic data on oligo- and polynucleotides will not be included here since these results have been tabulated and reviewed elsewhere [1–4]. Instead, selected data will be presented to help illustrate the relative merits of each experimental method described for extracting thermodynamic data from optical and calorimetric studies on oligonucleotides.
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Abbreviations
- K:
-
equilibrium constant
- K(Tm):
-
equilibrium constant at T m
- Tm:
-
melting temperature at α=0.5
- ΔHvH :
-
van’t Hoff enthalpy as derived from temperature dependence of equilibrium constant [kJ (mol of cooperative unit) - 1]
- ΔH con.depVH .:
-
van’ Hoff enthalpy calculated using Eq. (9)
- ΔH shapeVH :
-
van’t Hoff enthalpy calculated using Eq. (5) or (6)
- ΔH calVH :
-
van’t Hoff enthalpy calculated using Eq. (8)
- ΔHcal :
-
calorimetrically obtained molar enthalpy. The numerical value depends on the unit of the mol (strands or base pairs)
- ΔH 0cal :
-
calorimetrically obtained standard molar enthalpy
- ΔH:
-
transition enthalpy per mole of base pair stack
- ΔH 0obs :
-
observed standard transition enthalpy per mol of duplex
- ΔH 0pred :
-
predicted standard transition enthalpy per mol of duplex
- ΔH0 :
-
standard enthalpy change
- ΔG0 :
-
standard Gibbs energy change
- ΔS0 :
-
standard entropy change
- CT :
-
total strand concentration
- C iT :
-
total strand concentration of substance i
- C jT :
-
total strand concentration of substance j
- α:
-
fraction of oligonucleotide strands in the double-stranded state (degree of association)
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Breslauer, K.J. (1986). Methods for Obtaining Thermodynamic Data on Oligonucleotide Transitions. In: Hinz, HJ. (eds) Thermodynamic Data for Biochemistry and Biotechnology. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-71114-5_15
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