Overcoming Volume Selectivity of Dipolar Recoupling in Biological Solid‐State NMR Spectroscopy

• Published in: Angewandte Chemie International Edition Vol. 57; no. 44; pp. 14514 - 14518
• Main Authors: Tošner, Zdeněk, Sarkar, Riddhiman, Becker‐Baldus, Johanna, Glaubitz, Clemens, Wegner, Sebastian, Engelke, Frank, Glaser, Steffen J., Reif, Bernd
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 26-10-2018
• Edition: International ed. in English
• Subjects: Adiabatic; Aliphatic compounds; Biological properties; Biological samples; Carbonyls; Computer Simulation; dipolar recoupling; Inhomogeneity; Magnetic resonance spectroscopy; Magnetic Resonance Spectroscopy - methods; NMR spectroscopy; Optimal control; Proteins; Radio frequency; solid-state NMR spectroscopy; structural biology; volume selection; volume selection; optimal control; dipolar recoupling; structural biology; solid-state NMR spectroscopy
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201805002

Dipolar recoupling in solid‐state NMR is an essential method for establishing correlations between nuclei that are close in space. In applications on protein samples, the traditional experiments like ramped and adiabatic DCP suffer from the fact that dipolar recoupling occurs only within a limited volume of the sample. This selection is dictated by the radiofrequency (rf) field inhomogeneity profile of the excitation solenoidal coil. We employ optimal control strategies to design dipolar recoupling sequences with substantially larger responsive volume and increased sensitivity. We show that it is essential to compensate for additional temporal modulations induced by sample rotation in a spatially inhomogeneous rf field. Such modulations interfere with the pulse sequence and decrease its performance. Using large‐scale optimizations we developed pulse schemes for magnetization transfer from amide nitrogen to carbonyl (NCO) as well as aliphatic carbons (NCA). Our experiments yield a signal intensity increased by a factor of 1.5 and 2.0 for NCA and NCO transfers, respectively, compared to conventional ramped DCP sequences. Consistent results were obtained using several biological samples and NMR instruments.
Radiofrequency field inhomogeneity: Heteronuclear dipolar recoupling experiments with substantially larger responsive volume and increased sensitivity compared to the traditional Hartmann–Hahn sequences have been designed using optimal control strategies. Compensation is essential for temporal modulations induced by sample rotation in a spatially inhomogeneous radiofrequency field of a solenoidal coil.