Skip to main content

Research Repository

See what's under the surface

Advanced Search

Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP

Märker, Katharina; Paul, Subhradip; Fernández-de-Alba, Carlos; Lee, Daniel; Mouesca, Jean-Marie; Hediger, Sabine; De Paëpe, Gaël

Authors

Katharina Märker

Subhradip Paul

Carlos Fernández-de-Alba

Daniel Lee

Jean-Marie Mouesca

Sabine Hediger

Gaël De Paëpe



Abstract

The self-assembly of small organic molecules is an intriguing phenomenon, which provides nanoscale structures for applications in numerous fields from medicine to molecular electronics. Detailed knowledge of their structure, in particular on the supramolecular level, is a prerequisite for the rational design of improved self-assembled systems. In this work, we prove the feasibility of a novel concept of NMR-based 3D structure determination of such assemblies in the solid state. The key point of this concept is the deliberate use of samples that contain 13C at its natural isotopic abundance (NA, 1.1%), while exploiting magic-angle spinning dynamic nuclear polarization (MAS-DNP) to compensate for the reduced sensitivity. Since dipolar truncation effects are suppressed to a large extent in NA samples, unique and highly informative spectra can be recorded which are impossible to obtain on an isotopically labeled system. On the self-assembled cyclic diphenylalanine peptide, we demonstrate the detection of long-range internuclear distances up to ∼7 Å, allowing us to observe π-stacking through 13C–13C correlation spectra, providing a powerful tool for the analysis of one of the most important non-covalent interactions. Furthermore, experimental polarization transfer curves are in remarkable agreement with numerical simulations based on the crystallographic structure, and can be fully rationalized as the superposition of intra- and intermolecular contributions. This new approach to NMR crystallography provides access to rich and precise structural information, opening up a new avenue to de novo crystal structure determination by NMR.

Journal Article Type Article
Publication Date Feb 1, 2017
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 8
Issue 2
APA6 Citation Märker, K., Paul, S., Fernández-de-Alba, C., Lee, D., Mouesca, J., Hediger, S., & De Paëpe, G. (2017). Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP. Chemical Science, 8(2), https://doi.org/10.1039/C6SC02709A
DOI https://doi.org/10.1039/C6SC02709A
Publisher URL http://pubs.rsc.org/en/Content/ArticleLanding/2017/SC/C6SC02709A#!divAbstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by-nc/4.0

Files

Märker et al. - 2016 - Welcoming natural isotopic abundance in solid-state NMR probing π-stacking and supramolecular structure of organi.pdf (1.4 Mb)
PDF

Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by-nc/4.0





You might also like



Downloadable Citations

;