Concerted dynamics of metallo-base pairs in an A/B-form helical transition

Metal-mediated base pairs expand the repertoire of nucleic acid structures and dynamics. Here we report solution structures and dynamics of duplex DNA containing two all-natural C-Hg -T metallo base pairs separated by six canonical base pairs. NMR experiments reveal a 3:1 ratio of well-resolved stru...

Full description

Saved in:
Bibliographic Details
Published inNature communications Vol. 10; no. 1; pp. 4818 - 11
Main Authors Schmidt, Olivia P, Jurt, Simon, Johannsen, Silke, Karimi, Ashkan, Sigel, Roland K O, Luedtke, Nathan W
Format Journal Article
LanguageEnglish
Published England Nature Publishing Group 23.10.2019
Nature Publishing Group UK
Nature Portfolio
Subjects
Base Pairing
Base pairs
Bats
Bonding strength
Coupling (molecular)
Cytosine
Deoxyribonucleic acid
DNA
DNA - chemistry
DNA - ultrastructure
DNA, A-Form - chemistry
DNA, A-Form - ultrastructure
DNA, B-Form - chemistry
DNA, B-Form - ultrastructure
Helices
Ionization
Mercury - chemistry
Metallography
Metals
Models, Molecular
NMR
Nuclear magnetic resonance
Nucleic Acid Conformation
Nucleotide sequence
Proton Magnetic Resonance Spectroscopy
Solutions
Thymine
Transition metals
Online AccessGet full text

Cover

More Information
Summary:Metal-mediated base pairs expand the repertoire of nucleic acid structures and dynamics. Here we report solution structures and dynamics of duplex DNA containing two all-natural C-Hg -T metallo base pairs separated by six canonical base pairs. NMR experiments reveal a 3:1 ratio of well-resolved structures in dynamic equilibrium. The major species contains two (N3)T-Hg -(N3)C base pairs in a predominantly B-form helix. The minor species contains (N3)T-Hg -(N4)C base pairs and greater A-form characteristics. Ten-fold different J coupling constants ( N, Hg) are observed for (N3)C-Hg (114 Hz) versus (N4)C-Hg (1052 Hz) connectivities, reflecting differences in cytosine ionization and metal-bonding strengths. Dynamic interconversion between the two types of C-Hg -T base pairs are coupled to a global conformational exchange between the helices. These observations inspired the design of a repetitive DNA sequence capable of undergoing a global B-to-A-form helical transition upon adding Hg , demonstrating that C-Hg -T has unique switching potential in DNA-based materials and devices.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-019-12440-x