Dipolar recoupling sequences

New isotropic mixing sequences suitable for scalar correlation experiments in solids have been designed using symmetry principles similar to those employed in the construction of the C7 dipolar recoupling sequence. Compared with existing methods, the new isotropic mixing sequences are... 

To conclude this section on recoupling of homonuclear dipolar interactions under MAS conditions, a few general remarks seem in place. The performances of some of the homonuclear dipolar recoupling sequences discussed here have... 

Generating such a connectivity map for a solid requires additionally a resolution-enhancement technique, such as MAS. Such techniques, as discussed previously, suppress precisely the spin-spin interactions that the connectivity map is meant to reveal. Therefore, to combine multiple-quantum experiments with MAS, a pulse sequence which counteracts the averaging effect of MAS, thereby restoring the dipole coupling, must be implemented during excitation and reconversion of the 2-quantum coherence. A variety of such dipolar recoupling sequences currently exist, of varying levels of performance and complexity. 

Using the OPENCORE NMR spectrometer, standard solid-state NMR experiments have been demonstrated in Ref. 2. They include 1H-13C CPMAS with TPPM decoupling, 13C-15N dipolar recoupling under MAS, 1H FSLG, 13C-13C 2D exchange, and so on. Here we show two more examples, where the spectrometer was used to implement standard pulse sequences, but in somewhat demanding circumstances in terms of sensitivity. 

Fig. 2 (a) DRAMA pulse sequence (using % = t/2 = rr/4 in the text) and a representative calculated dipolar recoupled frequency domain spectrum (reproduced from [23] with permission), (b) RFDR pulse sequence inserted as mixing block in a 2D 13C-13C chemical shift correlation experiment, along with an experimental spectrum of 13C-labeled alanine (reproduced from [24] with permission), (c) Rotational resonance inversion sequence along with an n = 3 rotational resonance differential dephasing curve for 13C-labeled alanine (reproduced from [21] with permission), (d) Double-quantum HORROR experiment along with a 2D HORROR nutation spectrum of 13C2-2,3-L-alanine (reproduced from [26] with permission)... 

Fig. 5 Symmetry-based dipolar recoupling illustrated in terms of pulse sequences for the CN (a) and RNvn (b) pulse sequences, a spin-space selection diagram for the Cl symmetry (c) (reproduced from [118] with permission). Application of POST-CVj [31] as an element in a H- H double-quantum vs 13C chemical shift correlation experiment (d) used as elements (B panel) in a study of water binding to polycrystalline proteins (reproduced from [119] with permission)...

Fig. 21 HMQC pulse sequences for (a) 14N-13C and (b) 14N- H correlations under rotor-synchronized MAS. In (b), dipolar recoupling is usually applied during time intervals Texc and Trec. (c) Coherence transfer pathways for the observation of SQ (solid lines) and DQ (dashed lines) in the 14N dimension...

Dipolar recoupling with a windowless sequence (DRAWS)... 

Another offset-insensitive scheme, named DRAWS (dipolar recoupling with a windowless sequence), was proposed by Gregory et a/.157 It can be regarded as the windowless version of DRAMA, and it has the same DQ efficiency. Using the DQ build-up curves, the internuclear distance can be measured. 

The simplest technique that enables phosphorus-phosphorus correlations for complex multi-component system and elucidation of structural constraints is the PDSD sequence.48 This experiment is relatively easy to set up however, the distances between spins cannot be established with satisfactory precision. One common way of determining distance type information using spin-7i NMR is based on the acquisition of the DQ filtered spectra as a function of the DQ mixing time.49 The recently introduced DQ homonuclear recoupling sequences based on C and/or R symmetry developed by Levitt and co-workers allows very precise analysis of intemuclear distances.50 The accuracy of distances obtained from these DQ experiments depends on the effective suppression of contributions to the spin Hamiltonian other than the required homonuclear dipolar coupling terms. 

---