What governs the charge transfer in DNA? The role of DNA conformation and environment

J Phys Chem B. 2008 Jul 24;112(29):8788-98. doi: 10.1021/jp803661f. Epub 2008 Jun 27.

Abstract

Charge transfer in DNA has received much attention in the last few years due to its role in oxidative damage and repair in DNA and also due to possible applications of DNA in nanoelectronics. Despite intense experimental and theoretical efforts, the mechanism underlying long-range hole transport is still unresolved. This is in particular due to the sensitive dependence of charge transfer on the complex structure and dynamics of DNA and the interaction with the solvent, which could not be addressed adequately in the modeling approaches up to now. In this work, we study the factors governing hole transfer in detail, using a DFT-based fragment-orbital method, which allows to compute the charge transfer parameters along multinanosecond molecular dynamics simulations. Environmental effects are captured using a hybrid quantum mechanics-molecular mechanics (QM/MM) coupling scheme. This methodology allows to analyze several factors responsible for charge transfer in DNA in detail. The fluctuation of counterions, strongly counterbalanced by the surrounding water, leads to large oscillations of onsite energies, which govern the energetics of hole propagation along the DNA strand. In contrast, the electronic couplings depend only on DNA conformation and are not affected by the solvent. In particular, the onsite energies are strongly correlated between neighboring nucleobases, indicating that a conformational-gating type of mechanism may be induced by the collective environmental degrees of freedom.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Algorithms
  • Base Pairing
  • Computer Simulation*
  • DNA / chemistry*
  • Energy Transfer
  • Models, Molecular
  • Nucleic Acid Conformation*
  • Quantum Theory
  • Solvents / chemistry
  • Static Electricity
  • Thermodynamics
  • Time Factors
  • Water / chemistry

Substances

  • Solvents
  • Water
  • DNA