January 13, 2023
Journal Article

Sodium Cationization Enables Exotic Deprotonation Sites on Gaseous Mononucleotides


We report observation and photoelectron spectroscopic characterization of sodium cationization on four doubly deprotonated mononucleotide dianions Na+·[dNMP-2H]2- (N = A, G, C, or T) in the gas phase. Multiple tautomers with distinct deprotonated sites are identified, in which Na+ enables novel double deprotonation patterns and folds resultant mononucleotide dianions. The most stable isomer for the whole family is derived from detaching one proton from phosphate and the other from nucleobase (amino group for N = A, G and C, but nitrogen atom for T), while a high-lying isomer with protons detached separately from phosphate and hydroxy group of sugar coexist. Particularly, an exotic deprotomer with both protons deprived from guanosine is populated as well. This work thus displays a remarkably diverse binding landscape enabled by sodium cationization, a potentially critical element in developing general formulism to better model metal cation and nucleotide interactions.

Published: January 13, 2023


Yuan Q., W. Feng, W. Cao, Y. Zhou, L. Cheng, and X. Wang. 2022. Sodium Cationization Enables Exotic Deprotonation Sites on Gaseous Mononucleotides. The Journal of Physical Chemistry Letters 13, no. 42:9975–9982. PNNL-SA-178693. doi:10.1021/acs.jpclett.2c02691

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