Scalar coupled experiments

Scalar coupled experiments COSY and TOCSY The correlated spectroscopy (COSY) experiment is one of the most simple 2D-NMR pulse sequences in terms of the number of RF pulses it requires [32]. The basic sequence consists of a 90-C-90-acquire. The sequence starts with an excitation pulse followed by an evolution period and then an additional 90° pulse prior to acquisition. Once the time domain data are Fourier transformed, the data appear as a diagonal in... 

Di Bari L, Kowalewski J and Bodenhausen G 1990 Magnetization transfer modes in scalar-coupled spin systems investigated by selective 2-dimensional nuclear magnetic resonance exchange experiments J. Chem. Rhys. 93 7698-705... 

In a selective-inversion experiment, it is the relaxation of the z magnetizations that is being studied. For a system without scalar coupling, this is straightforward a simple pulse will convert the z magnetizations directly into observable signals. For a coupled spur system, this relation between the z magnetizations and the observable transitions is much more complex [22]. 

When performing 2D-NMR experiments one must keep in mind that the second frequency dimension (Fx) is digitized by the number of tx increments. Therefore, it is important to consider the amount of spectral resolution that is needed to resolve the correlations of interest. In the first dimension (F2), the resolution is independent of time relative to F. The only requirement for F2 is that the necessary number of scans is obtained to allow appropriate signal averaging to obtain the desired S/N. These two parameters, the number of scans acquired per tx increment and the total number of tx increments, are what dictate the amount of time required to acquire the full 2D-data matrix. 2D-homo-nuclear spectroscopy can be summarized by three different interactions, namely scalar coupling, dipolar coupling and exchange processes. 

In the alternative approach, the HN(i), 15N( j, 13C (i/i— 1) correlations in the HNCA-TROSY spectrum can be supplemented with the data from the HN(CO)CA-TROSY experiment72 73 yielding solely 11 IN(/), 15N( ), 13C (i- 1) correlations. To this end, the HNCO-TROSY experiment is extended with the 13C —> 13C INEPT step, which utilizes rather large (ca. 51-55 Hz) one-bond scalar coupling between the 13C and 13C spins in order to transfer magnetization from the 13C (< — 1) nucleus further to the 13C ( — 1) spin. 

As an example of the measurement of cross-correlated relaxation between CSA and dipolar couplings, we choose the J-resolved constant time experiment [30] (Fig. 7.26 a) that measures the cross-correlated relaxation of 1H,13C-dipolar coupling and 31P-chemical shift anisotropy to determine the phosphodiester backbone angles a and in RNA. Since 31P is not bound to NMR-active nuclei, NOE information for the backbone of RNA is sparse, and vicinal scalar coupling constants cannot be exploited. The cross-correlated relaxation rates can be obtained from the relative scaling (shown schematically in Fig. 7.19d) of the two submultiplet intensities derived from an H-coupled constant time spectrum of 13C,31P double- and zero-quantum coherence [DQC (double-quantum coherence) and ZQC (zero-quantum coherence), respectively]. These traces are shown in Fig. 7.26c. The desired cross-correlated relaxation rate can be extracted from the intensities of the cross peaks according to ... 

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