Ultrashort Broadband Cooperative Pulses for Multidimensional Biomolecular NMR Experiments

Abstract

NMR spectroscopy at ultra-high magnetic fields requires improved radiofrequency (rf) pulses to cover the increased spectral bandwidth. Optimized 90° pulse pairs were introduced as Ramsey-type cooperative (Ram-COOP) pulses for biomolecular NMR applications. The Ram-COOP element provides broadband excitation with enhanced sensitivity and reduced artifacts even at magnetic fields >1.0 GHz ¹ H Larmor frequency (23 T). A pair of 30 μs Ram-COOP pulses achieves an excitation bandwidth of 100 kHz with a maximum rf field of 20 kHz, more than three-fold improved compared to excitation by rectangular pulses. Ram-COOP pulses exhibit little offset-dependent phase errors and are robust to rf inhomogeneity. The performance of the Ram-COOP element is experimentally confirmed with heteronuclear multidimensional NMR experiments, applied to proteins and nucleic acids. Ram-COOP provides broadband excitation at low rf field strength suitable for application at current magnetic fields and beyond 23 T.

Keywords: HMQC; NOESY; cooperative broadband excitation pulses; high-field NMR spectroscopy; optimal control theory.