Optimum excitation of "enhanced" central transition populations.
Central transition (CT) sensitivity enhancement schemes that transfer polarization from satellites to the CT through selective saturation or inversion of neighboring satellite transitions have provided a welcome improvement for magic-angle spinning spectra of half-integer quadrupole nuclei. While many researchers have investigated and developed different methods of creating enhanced CT populations, here we investigate the conversion of these enhanced CT populations into observable CT coherence. We show a somewhat unexpected result that a conversion pulse length optimized for maximum sensitivity on equilibrium populations may not be optimum for an enhanced (non-equilibrium) polarization. Furthermore, CT enhancements can be lost if excessive rf field strength is used to convert this enhanced polarization into CT coherence. While a maximally enhanced CT signal is expected when using a perfectly selective CT conversion pulse, we have found that significant sensitivity loss can occur when using surprisingly low rf field strengths, even for sites with relatively large quadrupole coupling constants. We have systematically investigated these issues, and present some general guidelines and expectations when optimizing the conversion of enhanced (non-equilibrium) CT populations into observable CT coherence.
Trease
Nicole M
NM
Department of Chemistry, The Ohio State University, Columbus, OH 43210-1173, USA.
Dey
Krishna K
KK
Grandinetti
Philip J
PJ
D000465:Algorithms; D003198:Computer Simulation; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008956:Models, Chemical; D012680:Sensitivity and Specificity; D013113:Spin Labels
D013113:Spin Labels