By Gerd N. La Mar, Jeffrey S. de Ropp (auth.), Lawrence J. Berliner, Jacques Reuben (eds.)
The first of a quantity set, quantity 12 presents a long-awaited compilation of NMR idea to paramagnetic molecules. overseas specialists file the newest advancements in NMR technique as utilized to strongly secure and shifted resonances, aspect the theoretical facets of paramagnetic shift and rest, and talk about the interpretive bases of those molecular homes with regards to the constitution and serve as of varied paramagnetic molecules.
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Extra resources for NMR of Paramagnetic Molecules
Sample text
For small molecules, the paramagnetic suppression of NOEs is most effective (see Fig. 10 at negative log cor r ); moreover, many such molecules also have small negative NOEs due to being close to the region where NOEs change sign (Barbush and Dixon, 1985). , 1989). Estimation of p(para) is sufficient to determine the viscosity needed to yield detectable NOEs. Obviously the method will work better for compounds with small rather than large p(para). The addition of viscosity-increasing agents (ethylene glycol, glycerol, DMSO, glucose) to water may make NOEs more practical for small proteins with particularly effective paramagnetic relaxivities.
The general NOE for spin i upon saturating j is defined as: (18) where 10 , Jo are the equilibria magnetizations of i,j, and let) is the i spin magnetization some time t after perturbing spinj. The experiment is always carried out in the difference mode, where one spectrum is collected with spinj saturated (the decoupler on-resonance for spinj), which will be subtracted from another spectrum for which the decoupler is placed in some portion of the spectral window so as not to influence any spin in the system.
For p;{para) we have (Swift, 1973; Bertini and Luchinat, 1986): (16) where B = fs iP2 r2S(S + 1), C = ~S(S + 1), A is the Fermi contact coupling constant, and 1(,e), f' ('e) are functions of the electron spin correlation times whose form need not be specified for the analysis of differential dipolar relaxation via Eq. (3a). The contribution to the first term in Eq. (16) results from electron spin-nuclear dipole relaxation. The second term in Eq. (16) arises from scalar relaxation, makes a negligible contribution to p;{para), and can be neglected.