NMR in Molecular Biology by Oleg Jardetzky

By Oleg Jardetzky

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The form of the dependence of J on 0 is shown in Fig. 11-14. The Karplus relationship [Eq. (11-29)] suggests that it might be possible to determine conformations about any single bond that lies between two bonds connecting to atoms observable by N M R . "Karplus relations" 3 1 x have been developed for ^ N C ^ H , P O C H , and many other molecular fragments. These are discussed in Chapters V and VI since they have been used extensively in studies of the conformation of peptides, nucleotides, and other small molecules.

The relative contributions of a- and 7i-electrons to the magnitude of J in different systems, evaluated by the equations developed by Ramsey (1953) and McConnell (1956b), are to be understood as rough, rather than accurate, estimates. Nevertheless, some useful relationships between coupling constants and structural parameters have a semitheoretical basis. Among these, of greatest interest in biochemistry is the relationship between the magnitude of the coupling constants across three bonds (vicinal coupling constants) and the dihedral angle 0 about the central bonds (see Fig.

This is primarily of interest in organic chemistry and is treated adequately in books on chemical applications of NMR. In spectra containing several sets of multiplets it becomes necessary to establish which pairs of multiplets represent nuclei coupled to each other. This is readily done by a double irradiation or spin decoupling experiment 41 E. SPIN-SPIN COUPLING (Bloch, 1954). In the usual form of this experiment one multiplet is selectively irradiated at the frequency corresponding to its chemical shift, while the remainder of the spectrum is observed.

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