Efficient low-power heteronuclear decoupling in13C high-resolution solid-state NMR under fast magic angle spinning

Abstract

The use of a low-power two-pulse phase modulation (TPPM) sequence is proposed for efficient (1)H radio frequency (rf) decoupling in high-resolution (13)C solid-state NMR (SSNMR) under fast MAS conditions. Decoupling efficiency for different low-power decoupling sequences such as continuous-wave (cw), TPPM, XiX, and π-pulse (PIPS) train decoupling has been investigated at a spinning speed of 40 kHz for (13)C CPMAS spectra of uniformly (13)C- and (15)N-labeled L-alanine. It was found that the TPPM decoupling sequence, which was originally designed for high-power decoupling, provides the best decoupling efficiency at low power among all the low-power decoupling sequences examined here. Optimum performance of the low-power TPPM sequence was found to be obtained at a decoupling field intensity (ω(1)) of ~ω(R)/4 with a pulse flip angle of ~π and a phase alternation between ± [Symbol: see text]([Symbol: see text] = 20° ), where ω(R)/2π is the spinning speed. The sensitivity obtained for (13) CO(2)(-), (13)CH, and (13)CH(3) in L-alanine under low-power TPPM at ω(1)/2π of 10 kHz was only 5-15% less than that under high-power TPPM at ω(1) /2π of 200 kHz, despite the fact that only 0.25% of the rf power was required in low-power TPPM. Analysis of the (13)CH(2) signals for uniformly (13) C- and (15) N-labeled L-isoleucine under various low-power decoupling sequences also confirmed superior performance of the low-power TPPM sequence, although the intensity obtained by low-power TPPM was 61% of that obtained by high-power TPPM. (13)C CPMAS spectra of (13)C-labeled ubiquitin micro crystals obtained by low-power TPPM demonstrates that the low-power TPPM sequence is a practical option that provides excellent resolution and sensitivity in (13)C SSNMR for hydrated proteins.