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



Subhradip Paul


Daniel Lee

Jean-Marie Mouesca

Sabine Hediger


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.


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), 974-987.

Journal Article Type Article
Acceptance Date Oct 18, 2016
Online Publication Date Oct 19, 2016
Publication Date Feb 1, 2017
Deposit Date Aug 16, 2017
Publicly Available Date Aug 16, 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
Pages 974-987
Public URL
Publisher URL!divAbstract
Additional Information : This document is Similarity Check deposited; : Supplementary Information; : The Royal Society of Chemistry has an exclusive publication licence for this journal; OPEN ACCESS: This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0); : Single-blind; : Received 20 June 2016; Accepted 18 October 2016; Accepted Manuscript published 19 October 2016; Advance Article published 4 November 2016; Version of Record published 30 January 2017


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