Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP
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 ration...
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| Format: | Article |
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Royal Society of Chemistry
2017
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| Online Access: | https://eprints.nottingham.ac.uk/44934/ |
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| author | Märker, Katharina Paul, Subhradip Fernández-de-Alba, Carlos Lee, Daniel Mouesca, Jean-Marie Hediger, Sabine De Paëpe, Gaël |
| author_facet | Märker, Katharina Paul, Subhradip Fernández-de-Alba, Carlos Lee, Daniel Mouesca, Jean-Marie Hediger, Sabine De Paëpe, Gaël |
| author_sort | Märker, Katharina |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T19:57:24Z |
| format | Article |
| id | nottingham-44934 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:57:24Z |
| publishDate | 2017 |
| publisher | Royal Society of Chemistry |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-449342020-05-04T18:28:20Z https://eprints.nottingham.ac.uk/44934/ 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 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. Royal Society of Chemistry 2017-02-01 Article PeerReviewed Märker, Katharina, Paul, Subhradip, Fernández-de-Alba, Carlos, Lee, Daniel, Mouesca, Jean-Marie, Hediger, Sabine and De Paëpe, Gaël (2017) Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP. Chemical Science, 8 (2). pp. 974-987. ISSN 2041-6539 http://pubs.rsc.org/en/Content/ArticleLanding/2017/SC/C6SC02709A#!divAbstract doi:10.1039/C6SC02709A doi:10.1039/C6SC02709A |
| spellingShingle | Märker, Katharina Paul, Subhradip Fernández-de-Alba, Carlos Lee, Daniel Mouesca, Jean-Marie Hediger, Sabine De Paëpe, Gaël Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP |
| title | Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP |
| title_full | Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP |
| title_fullStr | Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP |
| title_full_unstemmed | Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP |
| title_short | Welcoming natural isotopic abundance in solid-state NMR: probing π-stacking and supramolecular structure of organic nanoassemblies using DNP |
| title_sort | welcoming natural isotopic abundance in solid-state nmr: probing π-stacking and supramolecular structure of organic nanoassemblies using dnp |
| url | https://eprints.nottingham.ac.uk/44934/ https://eprints.nottingham.ac.uk/44934/ https://eprints.nottingham.ac.uk/44934/ |