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Spectroscopic evidence for a gas-phase librating G-quartet-Na(+) complex.

C Fraschetti1, M Montagna, L Guarcini

  • 1Pharmaceutical Chemistry and Technologies, Sapienza-University of Rome, Piazzale Aldo Moro, 5, 00185, Rome, Italy. caterina.fraschetti@uniroma1.it.

Chemical Communications (Cambridge, England)
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Investigating G-quartet-sodium complexes using infrared multiphoton dissociation (IRMPD) spectroscopy and simulations revealed two stable forms. These conformers are separated by an energy barrier that allows easy interconversion at room temperature.

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Area of Science:

  • Biophysical chemistry
  • Structural biology
  • Computational chemistry

Background:

  • G-quadruplexes are four-stranded nucleic acid structures with significant biological roles.
  • Understanding the conformational dynamics of G-quadruplexes is crucial for their function.
  • Sodium ions are known to influence G-quadruplex stability and structure.

Purpose of the Study:

  • To investigate the conformational landscape of the G-quadruplex-Na(+) complex.
  • To characterize the stability and interconversion of different G-quadruplex conformers in the presence of sodium ions.

Main Methods:

  • Infrared multiphoton dissociation (IRMPD) spectroscopy was used to probe the G-quadruplex-Na(+) complex.
  • Ab initio molecular dynamics (AIMD) simulations were employed to model the conformational behavior and energy landscape.

Main Results:

  • IRMPD spectroscopy identified distinct conformeric populations of the G-quadruplex-Na(+) complex.
  • AIMD simulations revealed two metastable conformeric states separated by a free energy barrier.
  • This energy barrier is readily overcome at room temperature, indicating facile interconversion.

Conclusions:

  • The G-quadruplex-Na(+) complex exists in at least two distinct, metastable conformational states.
  • Conformational flexibility and interconversion are key features of G-quadruplexes in the presence of sodium ions.
  • These findings provide insights into the dynamic nature of G-quadruplex structures.