Interaction of Cu(+) with cytosine and formation of i-motif-like C-M(+)-C complexes: alkali versus coinage metals

Physical Chemistry Chemical Physics : PCCP
Juehan GaoJ Oomens

Abstract

The Watson-Crick structure of DNA is among the most well-known molecular structures of our time. However, alternative base-pairing motifs are also known to occur, often depending on base sequence, pH, or the presence of cations. Pairing of cytosine (C) bases induced by the sharing of a single proton (C-H(+)-C) may give rise to the so-called i-motif, which occurs primarily in expanded trinucleotide repeats and the telomeric region of DNA, particularly at low pH. At physiological pH, silver cations were recently found to stabilize C dimers in a C-Ag(+)-C structure analogous to the hemiprotonated C-dimer. Here we use infrared ion spectroscopy in combination with density functional theory calculations at the B3LYP/6-311G+(2df,2p) level to show that copper in the 1+ oxidation state induces an analogous formation of C-Cu(+)-C structures. In contrast to protons and these transition metal ions, alkali metal ions induce a different dimer structure, where each ligand coordinates the alkali metal ion in a bidentate fashion in which the N3 and O2 atoms of both cytosine ligands coordinate to the metal ion, sacrificing hydrogen-bonding interactions between the ligands for improved chelation of the metal cation.

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Citations

Sep 21, 2016·The Journal of Physical Chemistry. a·Juehan GaoJos Oomens
Jun 10, 2017·Chemical Reviews·Wenhu ZhouJuewen Liu
Jul 10, 2019·Journal of the American Society for Mass Spectrometry·L A HamlowM T Rodgers
Jan 21, 2020·Physical Chemistry Chemical Physics : PCCP·Ruodi ChengTravis D Fridgen
May 13, 2020·Physical Chemistry Chemical Physics : PCCP·Ruodi ChengTravis D Fridgen
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Dec 13, 2017·Physical Chemistry Chemical Physics : PCCP·Weibin RenJiang Zhao
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Jan 27, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Chunli SunFan Xia
Jan 12, 2021·Journal of the American Chemical Society·Samuel J P MarltonAdam J Trevitt
May 15, 2021·Journal of the American Chemical Society·Mingpan ChengJean-Louis Mergny
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Sep 7, 2019·The Journal of Physical Chemistry. a·Musleh Uddin MunshiJos Oomens
Sep 2, 2021·Nucleic Acids Research·Jeong Hwan HurKyeong Kyu Kim

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