Contact Ion Pairs of Phosphate Groups in Water -- Two-Dimensional Infrared Spectroscopy of Dimethyl-Phosphate and Ab-Initio Simulations

TL;DR

This study combines 2D-IR spectroscopy and ab-initio simulations to investigate contact ion pairs of dimethyl-phosphate with Na+, Ca2+, and Mg2+ in water, revealing structural differences and vibrational signatures.

Contribution

It provides new insights into the structure and vibrational properties of phosphate-ion contact pairs in water using combined experimental and theoretical methods.

Findings

Mg2+ forms the most compact contact pairs.

Ca2+ and Na+ contact pairs show wider structural variation.

Distinct vibrational signatures differentiate the contact geometries.

Abstract

The interaction of phosphate groups with ions in an aqueous environment has a strong impact on the structure and folding processes of DNA and RNA. The dynamic variety of ionic arrangements, including both contact pairs and water separated ions, and the molecular coupling mechanisms are far from being understood. In a combined experimental and theoretical approach, we address the properties of contact ion pairs of the prototypical system dimethyl-phosphate with Na$^+$, Ca$^{2+}$, and Mg$^{2+}$ ions in water. Linear and femtosecond two-dimensional infrared (2D-IR) spectroscopy of the asymmetric (PO$_2$)$^-$ stretching vibration separates and characterizes the different species via their blue-shifted vibrational signatures and 2D-IR lineshapes. Phosphate-magnesium contact pairs stand out as the most compact geometry while the contact pairs with Ca$^{2+}$ and Na$^+$ display a wider structural variation. Microscopic density functional theory simulations rationalize the observed frequency shifts and reveal distinct differences between the contact geometries.