Effects of L-spin longitudinal quadrupolar relaxation in S[L] heteronuclear recoupling and S-spin magic-angle spinning NMR.

In experiments on S-L heteronuclear spin systems with evolution of the S-spin magnetization under the influence of a quadrupolar nucleus (L-spin), effects of longitudinal quadrupolar (T(1Q)) relaxation of the L-spin coherence on the sub-millisecond time scale have been documented and explored, and methods for minimizing their effect have been demonstrated. The longitudinal relaxation results in heteronuclear dephasing even in the reference signal S(0) of S[L] REDOR, REAPDOR, RIDER, or SPIDER experiments, due to T(1Q)-relaxation of the transiently generated S(y)L(z) coherence, reducing or even eliminating the observable dephasing DeltaS. Pulse sequences for measuring an improved reference signal S(00) with minimal heteronuclear recoupling but the same number of pulses as for S(0) and S have been demonstrated. From the observed intensity DeltaS(0)=S(00)-S(0) and the SPIDER signal DeltaS/S(0), T(1Q) can be estimated. Accelerated decays analogous to the dipolar S(0) curves will occur in T(2) measurements for J-coupled S-L spin pairs. Even in the absence of recoupling pulses, fast T(1Q) relaxation of the unobserved nucleus shortens the transverse relaxation time T(2S,MAS) of the observed nucleus, in particular at low spinning frequencies, due to unavoidable heteronuclear dipolar evolution during a rotation period. The observed spinning-frequency dependence of T(2S,MAS) matches the theoretical prediction and may be used to estimate T(1Q). The effects are demonstrated on several (13)C[(14)N] spin systems, including an arginine derivative, the natural N-acetylated polysaccharide chitin, and a model peptide, (POG)(10).