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The relationship between rate of exchange and the diffusion period at which the DOSY data is collected can impact the diffusion coefficient of each exchangeable proton on the observed species. If a proton behaves more "clusterlike" over the diffusion time, the diffusion coefficient associated with the peak in question will be more clusterlike in character and hence shifted towards the peak in question (e.g., the cluster). If the proton is acting more "waterlike" the diffusion coefficient will shift closer to water. The degree of this shift depends on the rate of exchange. Protons on the cluster that are in faster exchange will appear to have larger diffusion coefficients, which causes a large spread in the measured cluster diffusion coefficents, and hence, hydrodynamic radii. For a detailed discussion in the context of the DOSY spectra of sucrose, see:, SS 127
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Preparation of a Series of Heteromentallic Aqueous Tridecameric Clusters
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