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Electron Attachment to Wobble Base Pairs.

Jishnu Narayanan S J1, Arnab Bachhar1, Divya Tripathi1

  • 1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai400076, India.

The Journal of Physical Chemistry. A
|January 9, 2023
PubMed
Summary
This summary is machine-generated.

Electron attachment to wobble base pairs occurs via a doorway mechanism involving dipole-bound anions. This process, slower than in Watson-Crick pairs, involves proton transfer in specific base pairs like hypoxanthine-cytosine.

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Area of Science:

  • Quantum chemistry
  • Biophysics
  • Molecular biology

Background:

  • Wobble base pairs are crucial in nucleic acid structure and function.
  • Understanding electron attachment mechanisms is vital for comprehending DNA stability and repair.
  • Previous studies have explored electron interactions with Watson-Crick base pairs.

Purpose of the Study:

  • To investigate the low-energy electron attachment mechanism to wobble base pairs.
  • To elucidate the role of dipole-bound anions and proton transfer in this process.
  • To compare the electron attachment rate in wobble base pairs with that of Watson-Crick pairs.

Main Methods:

  • Utilized the equation of motion coupled cluster method.
  • Employed extended basis sets for accurate calculations.
  • Analyzed the transition dynamics from dipole-bound to valence-bound anionic states.

Main Results:

  • Identified a doorway mechanism for electron attachment, initiated by dipole-bound anions.
  • Observed the formation of valence-bound anions through the mixing of electronic and nuclear degrees of freedom.
  • Found that proton transfer accompanies anion formation in hypoxanthine-cytosine and hypoxanthine-adenine pairs.
  • Calculated a slower rate constant for the dipole-bound to valence-bound transition in wobble base pairs compared to guanine-cytosine.

Conclusions:

  • The electron attachment to wobble base pairs proceeds through a distinct doorway mechanism.
  • Proton transfer is intrinsically linked to valence-bound anion formation in specific wobble pairs.
  • Wobble base pairs exhibit a reduced efficiency in electron attachment compared to Watson-Crick pairs, potentially impacting DNA dynamics.