Broadband Relaxation-Optimized Polarization Transfer in Magnetic Resonance

Many applications of magnetic resonance are limited by rapid loss of spin coherence caused by large transverse relaxation rates. In nuclear magnetic resonance (NMR) of large proteins, increased relaxation losses lead to poor sensitivity of experiments and increased measurement time. In this paper we develop broadband relaxation optimized pulse sequences (BB-CROP) which approach fundamental limits of coherence transfer efficiency in the presence of very general relaxation mechanisms that include cross-correlated relaxation. These broadband transfer schemes use new techniques of chemical shift refocusing (STAR echoes) that are tailored to specific trajectories of coupled spin evolution. We present simulations and experimental data indicating significant enhancement in the sensitivity of multi-dimensional NMR experiments of large molecules by use of these methods.