Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 118, Issue 21, Pages 3804-3809Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp5038969
Keywords
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Funding
- ECOS-MinCyT cooperation program [A11E02]
- FONCyT
- CONICET
- SeCyT-UNC
- European Community [226716]
- CNRS
- Universite Paris-Sud
- University Paris-Sud
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The study of metal ion-DNA interaction aiming to understand the stabilization of artificial base pairing and a number of noncanonical motifs is of current interest, due to their potential exploitation in developing new technological devices and expanding the genetic code. A successful strategy has been the synthesis of metal-mediated base pairs, in which a coordinative bond to a central metal cation replaces a H-bond in a natural pair. In this work, we characterized, for the first time, the gas phase structure of the cytosine center dot center dot center dot Ag+center dot center dot center dot cytosine (C-Ag+-C) complex by means of InfraRed-MultiPhoton-Dissociation (IR-MPD) spectroscopy and theoretical calculation. The IR-spectrum was confidently assigned to one structure with the Ag+ acting as a bridge between the heteronitrogen atoms in each cytosine (both in the keto-amino form). This structure is biologically relevant since it mimics the structure of the hemiprotonated C-H+-C dimer responsible for the stabilization of the i-motif structure in DNA, with the replacement of the NH center dot center dot center dot N bond by a stronger N center dot center dot center dot Ag+center dot center dot center dot N bond. Moreover, since the structure of the C-Ag+-C complex is planar, it allows an optimum intercalation between pairs of the two antiparallel strand duplex in the DNA i-motif structure.
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