High-resolution DOSY NMR with spins in different chemical surroundings: influence of particle exchange.

The effect of chemical exchange in the diffusion-ordered (DOSY) spectra of a two-site system in the slow-exchange limit with respect to the chemical shift is studied. The problem is addressed both theoretically and experimentally. The relationship between diffusion time (t) and mean lifetimes (tau) is studied by the simulation of the magnetization attenuations as a function of the gradient strength, under PFG conditions. The influence of the difference in populations and diffusion coefficients of the two sites is also considered. In analogy to the limiting cases of fast- and slow-exchange with respect to the chemical shift, limiting cases with respect to the diffusion dimension are defined. The slow-exchange limit in diffusion corresponds to the relation of t and tau that allows us to observe the two spins in exchange associated with the individual diffusion coefficients of the two sites when no exchange is present. The fast-exchange limit in diffusion is reached when the relation of t and tau is such that the two spins present the same apparent diffusion coefficient. By using a model system consisting of water/t-butanol it is shown that by recording several DOSY experiments with increasing diffusion times it is possible to estimate the value of the exchange rate.