Polarization transfer, dipolar coupling

DQ coherence between C (,-) and C m and then let the DQ coherence evolve under the influence of the heteronuclear I3C-15N dipole-dipole interaction [181, 182]. The virtue of this design is that it can be easily combined with other resolution enhancement technique such as INADEQUATE [183]. Alternatively, the magnetization of C (,) dephased under the 13C-15N dipolar coupling can be transferred to C (j) for another period of 13C-15N dipolar dephasing [183]. This idea can be combined with the NCOCA experiment so that the superior resolution provided by the C (,-)-N(j+i) correlation could be exploited. The overall efficiency, however, is relatively low due to the use of two polarization-transfer steps, viz. 15N —> 13C and 13C —> 13C [183]. In comparison with the techniques, the advan-... 

Fig. 10.22. Diagram showing the cross-polarization from protons, H, to a heteronucleus, X, such as carbons. Heteronuclear dipolar coupling enables the transfer of magnetization from H to X, such as protons to carbons. Homonuclear dipolar coupling between the abundant protons enables the redistribution of proton spin energy through spin diffusion.

In the following, we will discuss heteronuclear polarization-transfer techniques in four different contexts. They can be used as a polarization-transfer method to increase the sensitivity of a nucleus and to shorten the recycle delay of an experiment as it is widely used in 1H-13C or 1H-15N cross polarization. Heteronuclear polarization-transfer methods can also be used as the correlation mechanism in a multi-dimensional NMR experiment where, for example, the chemical shifts of two different spins are correlated. The third application is in measuring dipolar coupling constants in order to obtain distance information between selected nuclei as is often done in the REDOR experiment. Finally, heteronuclear polarization transfer also plays a role in measuring dihedral angles by generating heteronuclear double-quantum coherences. 

Properties of the selective pulses are used therefore twofold in such experiments. Firstly, a selective pulse selectively perturbs the selected spin and the perturbation is distributed in the course of the experiment among the coupled spins, depending on the type of coupling (scalar, dipolar) and depending on the type of exchange mechanism (polarization transfer, cross polarization or cross relaxation). Secondly, the phase (selective 90° pulse) or the frequency (selective 180° pulse) of the selective pulse serve to label the response of both the selected and the residual coupled spins as positive or negative. 

The first combined 13C- H MAS/CP experiment was performed by Schaefer and Stejskal (23). The double-resonance procedure decouples the strong heteronuclear dipolar interactions and indirect J couplings, while the weak 13C signal is enhanced by proton polarization transfer. The residual spectral width of several kHz arises from 13C chemical shift anistropy and weak 13C- 3C dipolar interactions between 1.1 % abundant 13C nuclei. Both of these interactions are removed by MAS. 

Historically, Hartmann-Hahn polarization transfer was first applied to systems in the solid state (Slichter, 1978 Ernst et al., 1987), even though, in their seminal paper, Hartmann and Hahn (1962) reported applications to liquid samples. In general, Hartmann-Hahn experiments in the solid and liquid states differ with regard to the coupling mechanism (dipolar or indirect electron-mediated J coupling), the magnitude of the coupling... 

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