Direct Detection of Hydrogen Bonds in Supramolecular Systems Using 1 H- 15 N Heteronuclear Multiple Quantum Coherence Spectroscopy

• Published in: Journal of the American Chemical Society 2022-12, Vol.144 (50), p.23127-23133
• Main Authors: Jinks, Michael A, Howard, Mark, Rizzi, Federica, Goldup, Stephen M, Burnett, Andrew D, Wilson, Andrew J
• Format: Article
• Language: English
• Subjects: Hydrogen; Hydrogen Bonding; Magnetic Resonance Spectroscopy - methods; Protein Conformation
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.2c10742

Hydrogen-bonded supramolecular systems are usually characterized in solution through analysis of NMR data such as complexation-induced shifts and nuclear Overhauser effects (nOe). Routine direct detection of hydrogen bonding particularly in multicomponent mixtures, even with the aid of 2D NMR experiments for full assignment, is more challenging. We describe an elementary rapid H- N HMQC NMR experiment which addresses these challenges without the need for complex pulse sequences. Under readily accessible conditions (243/263 K, 50 mM solutions) and natural N abundance, unambiguous assignment of N resonances facilitates direct detection of intra- and intermolecular hydrogen bonds in mechanically interlocked structures and quadruply hydrogen-bonded dimers─of dialkylaminoureidopyrimidinones, ureidopyrimidinones, and diamidonaphthyridines─in single or multicomponent mixtures to establish tautomeric configuration, conformation, and, to resolve self-sorted speciation.