TY - JOUR

T1 - The effect of solvation on the radiation damage rate constants for adenine

AU - Milhøj, Birgitte Olai

AU - Sauer, Stephan P. A.

PY - 2016

Y1 - 2016

N2 - It is a well known fact, that water plays an important part in almost all biological systems and that inclusion of solvation effects might therefore be of utmost importance in studies of radiation damage to DNA. In the present investigation we have studied the effect of different solvation models in calculations of Gibbs free energies and reaction rates for the reaction between the OH radical and the DNA nucleobase adenine using Density Functional Theory at the ωB97X-D/6-311++G(2df,2pd) level with the Eckart tunneling correction. The solvent, water, has been included through either the implicit polarizable continuum model (PCM) or through explicit modelling of micro-solvation by a single water molecule at the site of reaction as well as the combination of both. Scrutiny of the thermodynamics and kinetics of the individual sub-reactions suggests that the qualitative differences introduced by the solvation models do not significantly alter the conclusions made based solely on simple gas phase calculations. Abstraction of the amine hydrogens H61 and H62 and addition onto C8 are still the most likely reaction pathways.

AB - It is a well known fact, that water plays an important part in almost all biological systems and that inclusion of solvation effects might therefore be of utmost importance in studies of radiation damage to DNA. In the present investigation we have studied the effect of different solvation models in calculations of Gibbs free energies and reaction rates for the reaction between the OH radical and the DNA nucleobase adenine using Density Functional Theory at the ωB97X-D/6-311++G(2df,2pd) level with the Eckart tunneling correction. The solvent, water, has been included through either the implicit polarizable continuum model (PCM) or through explicit modelling of micro-solvation by a single water molecule at the site of reaction as well as the combination of both. Scrutiny of the thermodynamics and kinetics of the individual sub-reactions suggests that the qualitative differences introduced by the solvation models do not significantly alter the conclusions made based solely on simple gas phase calculations. Abstraction of the amine hydrogens H61 and H62 and addition onto C8 are still the most likely reaction pathways.

KW - Faculty of Science

KW - Radiation Damage

KW - DNA Damage

KW - OH radical

KW - Adenine

KW - Density functional theory

KW - Kinetics

KW - DFT calculations

U2 - 10.1002/cphc.201600533

DO - 10.1002/cphc.201600533

M3 - Journal article

C2 - 27384247

VL - 17

SP - 3086

EP - 3095

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

IS - 19

ER -