Skip to Main content Skip to Navigation
Journal articles

Self‐Assembly of DNA and RNA Building Blocks Explored by Nitrogen‐14 NMR Crystallography: Structure and Dynamics

Abstract : The isotopic enrichment of nucleic acids with nitrogen-15 is often carried out by solid-phase synthesis of oligonucleotides using phosphoramidite precursors that are synthetically demanding and expensive. These synthetic challenges, combined with the overlap of chemical shifts, explain the lag of nitrogen-15 NMR studies of nucleic acids behind those of proteins. For the structural characterization of DNA and RNA-related systems, new NMR methods that exploit the naturally occurring 99.9 % abundant nitrogen-14 isotope are therefore highly desirable. In this study, we have investigated nitrogen-14 spectra of self-assembled quartets based on the nucleobase guanine in the solid state by means of magic-angle spinning NMR spectroscopy. The network of dipolar proton-nitrogen couplings between neighboring stacked purine units is probed by 2D spectra based on 1 H→14 N→1 H double cross-polarization. Interplane dipolar contacts are identified between the stacked G quartets. The assignment is supported by density functional theory (DFT) calculations of the anisotropic chemical shifts and quadrupolar parameters. The experimental spectra are fully consistent with internuclear distances obtained in silico. Averaging of chemical shifts due to internal motions can be interpreted by semiempirical calculations. This method can easily be extended to synthetic G quartets based on nucleobase or nucleoside analogs and potentially to oligonucleotides.
Complete list of metadatas

Cited literature [98 references]  Display  Hide  Download

https://hal-pasteur.archives-ouvertes.fr/pasteur-02625685
Contributor : Marcel Hollenstein <>
Submitted on : Tuesday, June 23, 2020 - 2:09:19 PM
Last modification on : Wednesday, October 14, 2020 - 3:41:06 AM
Long-term archiving on: : Thursday, September 24, 2020 - 5:15:56 PM

File

Manuscript_revised.pdf
Files produced by the author(s)

Identifiers

Citation

Diego Carnevale, Marcel Hollenstein, Geoffrey Bodenhausen. Self‐Assembly of DNA and RNA Building Blocks Explored by Nitrogen‐14 NMR Crystallography: Structure and Dynamics. ChemPhysChem, Wiley-VCH Verlag, 2020, 21 (10), pp.1044-1051. ⟨10.1002/cphc.201901214⟩. ⟨pasteur-02625685⟩

Share

Metrics

Record views

78

Files downloads

109