Hydrogen bonding between nucleobases produces diverse DNA structural motifs, including canonical duplexes, guanine (G) quadruplexes and cytosine (C) i-motifs. Incorporating metal-mediated base pairs into nucleic acid structures can introduce new functionalities and enhanced stabilities. Here we demonstrate, using mass spectrometry (MS)  and fluorescence resonance energy transfer (FRET), that parallel-stranded structures consisting of up to 20 G-Ag(I)-G or 30 C-Ag(I)-C contiguous base pairs are formed when natural DNA sequences are mixed with silver cations in aqueous solution.  Silver-mediated G-duplexes form preferentially over G-quadruplexes, and the ability of Ag+ to convert G-quadruplexes into silver-paired duplexes may provide a new route to manipulating these biologically relevant structures. Ion mobility spectrometry (IMS ) indicates that G-duplexes are linear and more rigid than B-DNA. DFT calculations were used to propose structures compatible with the IMS experiments. Such inexpensive, defect-free and soluble DNA-based nanowires open new directions in the design of novel metal-mediated DNA nanotechnology.
Hydrogen bonding between nucleobases produces diverse DNA structural motifs, including canonical duplexes, guanine (G) quadruplexes and cytosine (C) i-motifs. Incorporating metal-mediated base pairs into nucleic acid structures can introduce new functionalities and enhanced stabilities. Here we demonstrate, using mass spectrometry (MS) , ion mobility spectrometry (IMS) and fluorescence resonance energy transfer (FRET), that parallel-stranded structures consisting of up to 20 G-Ag(I)-G contiguous base pairs are formed when natural DNA sequences are mixed with silver cations in aqueous solution. FRET indicates that duplexes formed by poly(cytosine) strands with 20 contiguous C-Ag(I)-C base pairs are also parallel. Silver-mediated G-duplexes form preferentially over G-quadruplexes, and the ability of Ag+ to convert G-quadruplexes into silver-paired duplexes may provide a new route to manipulating these biologically relevant structures. IMS indicates that G-duplexes are linear and more rigid than B-DNA. DFT calculations were used to propose structures compatible with the IMS experiments. Such inexpensive, defect-free and soluble DNA-based nanowires open new directions in the design of novel metal-mediated DNA nanotechnology.
A
, ion mobility spectrometry (IMS)
D
or 30 C-Ag(I)-C
A
FRET indicates that duplexes formed by poly(cytosine) strands with 20 contiguous C-Ag(I)-C base pairs are also parallel.
R
Ion mobility spectrometry (IMS )
IMS