³⁵ Cl-¹ H Heteronuclear correlation magic-angle spinning nuclear magnetic resonance experiments for probing...

Heteronuclear multiple-quantum coherence (HMQC) pulse sequences for establishing heteronuclear correlation in solid-state nuclear magnetic resonance (NMR) between ³⁵ Cl and ¹ H nuclei in chloride salts under fast (60 kHz) magic-angle spinning (MAS) and at high magnetic field (a ¹ H Larmor frequency of 850 MHz) are investigated. Specifically, recoupling of the ³⁵ Cl-¹ H dipolar interaction using rotary resonance recoupling with phase inversion every rotor period or the symmetry-based SR4² ₁ pulse sequences are compared. In our implementation of the population transfer (PT) dipolar (D) HMQC experiment, the satellite transitions of the ³⁵ Cl nuclei are saturated with an off-resonance WURST sweep, at a low nutation frequency, over the second spinning sideband, whereby the WURST pulse must be of the same duration as the recoupling time. Numerical simulations of the ³⁵ Cl-¹ H MAS D-HMQC experiment performed separately for each crystallite orientation in a powder provide insight into the orientation dependence of changes in the second-order quadrupolar-broadened ³⁵ Cl MAS NMR lineshape under the application of dipolar recoupling. Two-dimensional ³⁵ Cl-¹ H PT-D-HMQC MAS NMR spectra are presented for the amino acids glycine·HCl and l-tyrosine·HCl and the pharmaceuticals cimetidine·HCl, amitriptyline·HCl and lidocaine·HCl·H₂ O. Experimentally observed ³⁵ Cl lineshapes are compared with those simulated for ³⁵ Cl chemical shift and quadrupolar parameters as calculated using the gauge-including projector-augmented wave (GIPAW) method: the calculated quadrupolar product (P_Q ) values exceed those measured experimentally by a factor of between 1.3 and 1.9.