A Nuclear Magnetic Resonance Investigation of the Energetics of Basepair Opening Pathways in DNA
| Autor: | Irina M. Russu, Daniel Coman |
|---|---|
| Rok vydání: | 2005 |
| Předmět: |
Hot Temperature
Magnetic Resonance Spectroscopy DNA Repair Proton Protein Conformation Base pair Molecular Sequence Data Enthalpy Biophysics Nucleic Acid Denaturation 010402 general chemistry 01 natural sciences Catalysis 03 medical and health sciences Protein structure Nuclear magnetic resonance Ammonia Nucleic Acids Base Pairing Equilibrium constant 030304 developmental biology Base Composition 0303 health sciences Base Sequence Chemistry Temperature DNA replication DNA Nuclear magnetic resonance spectroscopy 0104 chemical sciences Kinetics Oligodeoxyribonucleotides Nucleic Acid Conformation Thermodynamics Protons |
| Zdroj: | Biophysical Journal. 89(5):3285-3292 |
| ISSN: | 0006-3495 |
| DOI: | 10.1529/biophysj.105.065763 |
| Popis: | The opening of basepairs plays a key role in DNA replication and transcription, and in the action of DNA repair and modification enzymes. In this article, we have used proton exchange to define the energetics of the pathways for basepair opening in two DNA 17-mer duplexes. The rates of exchange of imino protons with solvent protons were measured by NMR spectroscopy for each DNA duplex, as a function of the concentration of exchange catalyst and of temperature. The measurements provided the rates and the equilibrium constants of the opening reactions for individual basepairs at different temperatures. These temperature dependences were used to calculate the enthalpies and the free energies of the barrier to opening and of the open state for each basepair. The results reveal the existence of three distinct patterns of enthalpy changes in the opening reactions. The patterns differ from each other in the location of the kinetic opening barrier relative to the open state. Neighboring bases, which are one or more positions removed from the opening basepair, influence the enthalpic pattern of the opening pathway. The free energies of the opening barriers are found to be linearly related to the free energies of the open state. This correlation is analyzed in terms of rate-equilibrium free energy relationships previously observed in other systems, and suggests that the transition state in the opening reaction is closer to the native closed state of the basepair than to its open state. |
| Databáze: | OpenAIRE |
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