Paramagnetic DOSY: An Accurate Tool for the Analysis of the Supramolecular Interactions between Lanthanide Complexes and Proteins

• Published in: Chemistry : a European journal 2016-12, Vol.22 (50), p.18123-18131
• Main Authors: Denis-Quanquin, Sandrine, Riobé, François, Delsuc, Marc-André, Maury, Olivier, Giraud, Nicolas
• Format: Article
• Language: English
• Subjects: Affinity; Chemical Sciences; Chemistry; Diffusion; Diffusion coefficient; diffusion-ordered NMR; Inorganic chemistry; Lanthanides; Material chemistry; Nuclear magnetic resonance; Organic chemistry; paramagnetism; protein; Proteins; supramolecular chemistry; Titration
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201603460

Diffusion ordered NMR is implemented to determine accurately the mobility of paramagnetic tris‐dipicolinate lanthanide complexes that are versatile probes of protein structure. It is shown that diffusion coefficient ratios can be measured with an accuracy of 1 % using a standard BPPLED pulse sequence, which allows for observing significant, though weak, variations when different species are interacting with the paramagnetic compound. We demonstrate that this approach is complementary to classical chemical shift titration experiments, and that it can be applied successfully to probe the supramolecular dynamic interactions between lanthanide complexes and small molecules on the one hand, or to determine rapidly their affinity for a targeted protein. Precision with diffusion: The implementation of diffusion‐ordered NMR techniques to accurately determine the mobility of paramagnetic tris‐dipicolinate lanthanide complexes is reported. The observed diffusion coefficients can be used to efficiently probe their affinity for a wide range of molecules ranging from small model compounds to proteins.