Consideration of the effect of heat capacity in the analysis of thermodynamics of formation of self-complementary deoxyoligonucleotide duplexes in aqueous solution
Keywords:
oligonucleotide, nucleic acid, DNA, self-association, chemical shift, heat capacity, enthalpy, NMR spectroscopyAbstract
Thermodynamics of formation of self-complementary deoxyoligonucleotide duplexes 5'-d(TpGpCpA), 5'-d(ApGpCpT), 5'-d(CpGpCpG), 5'-d(GpCpGpC), 5'-d(CpGpCpGpCpG), 5'-d(CpGpTpApCpG) and 5'-d(GpCpApTpGpC), in aqueous solution has been studied by the method of 1H NMR spectroscopy (500 MHz). Thermodynamical parameters have been determined using temperature dependences of proton chemical shifts of the oligomers and the theoretical model, taking into consideration the finite value of the heat capacity change and the temperature dependence of the enthalpy of duplex formation. The mean value of heat capacity change of duplex formation of the investigated deoxyoligonucleotide sequences, <delta Cp>=-(86±32) cal/(mol base pairs K), is in good agreement with experimental data, obtained by calorimetric methods for longer deoxyoligonucleotides and polynucleotide sequences.
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