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By G.L. James

ISBN-10: 0901223832

ISBN-13: 9780901223838

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Additional resources for Geometrical theory of diffraction for electromagnetic waves

Example text

In discussions so far we have referred to events as ranging from slow to fast on the chemical shift timescale since it is chemical shift differences that defined these exchange regimes. Typically, the phrase ‘NMR timescale’ will refer to the chemical shift timescale. Since chemical shift separations typically range from a few hertz up to a few kilohertz, dynamic NMR lineshape studies are most often sensitive to relatively slow equilibria occurring on second to millisecond timescales. 3. It is equally possible to consider events on a coupling constant timescale where the magnitudes of these provide the frequency reference; see discussions involving scalar coupling below.

Before we proceed further we consider briefly why dynamic exchange should lead to the broadening of resonances at all. 3). We also note that the observed resonance peak for each site arises from the summed intensity of all similar spins in the NMR sample, precessing with a similar frequency. Under conditions of two-site exchange, the change in environment from one site to another leads to the frequency of a spin to jump between two different values whenever an exchange event occurs. If this were to occur so infrequently that a complete FID can be collected before such a jump were to happen, then each spin will exhibit only a single frequency and the exchange process would be too slow to influence the NMR spectrum.

The most common reagents are chromium(III) acetylacetonate (Cr(acac)3), for organic solvents and manganese(II) chloride or gadolinium(III) chloride for aqueous solutions. Paramagnetic relaxation enhancement is also considered in the chapter Protein-Ligand Screening by NMR as a method to aid the detection of protein–ligand binding interactions. 3 Chemical Shift Anisotropy Relaxation The electron distribution in chemical bonds is inherently unsymmetrical or anisotropic and, as a result, the local field experienced by a nucleus, and hence its chemical shift, will depend on the orientation of the bond relative to the applied static field.

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