CHHC and (1)H-(1)H magnetization exchange: analysis by experimental solid-state NMR and 11-spin density-matrix...

A protocol is presented for correcting the effect of non-specific cross-polarization in CHHC solid-state MAS NMR experiments, thus allowing the recovery of the (1)H-(1)H magnetization exchange functions from the mixing-time dependent buildup of experimental CHHC peak intensity. The presented protocol also incorporates a scaling procedure to take into account the effect of multiplicity of a CH(2) or CH(3) moiety. Experimental CHHC buildup curves are presented for l-tyrosine.HCl samples where either all or only one in 10 molecules are U-(13)C labeled. Good agreement between experiment and 11-spin SPINEVOLUTION simulation (including only isotropic (1)H chemical shifts) is demonstrated for the initial buildup (t(mix)<100micros) of CHHC peak intensity corresponding to an intramolecular close (2.5A) H-H proximity. Differences in the initial CHHC buildup are observed between the one in 10 dilute and 100% samples for cases where there is a close intermolecular H-H proximity in addition to a close intramolecular H-H proximity. For the dilute sample, CHHC cross-peak intensities tended to significantly lower values for long mixing times (500micros) as compared to the 100% sample. This difference is explained as being due to the dependence of the limiting total magnetization on the ratio N(obs)/N(tot) between the number of protons that are directly attached to a (13)C nucleus and hence contribute significantly to the observed (13)C CHHC NMR signal, and the total number of (1)H spins into the system. (1)H-(1)H magnetization exchange curves extracted from CHHC spectra for the 100% l-tyrosine.HCl sample exhibit a clear sensitivity to the root sum squared dipolar coupling, with fast buildup being observed for the shortest intramolecular distances (2.5A) and slower, yet observable buildup for the longer intermolecular distances (up to 5A).