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The magnetization exchange between two groups of equivalent spins each havingdifferent populations and overall relaxation rates has been analyzed. The results suggest that either the spin population difference or the overall relaxation rate difference in an exchange spectrum can produce cross-peaks with volumes larger than that of the corresponding diagonal line. This is important for interpretation of the magnetization exchange between water and macromolecular protons where both the population differences and auto-relaxation rate differences can be very large. Theoretical predictions of peak volume evolutionwere experimentally verified in the intermolecular magnetization exchange between the water and labile amide proton in a model system N-acetylglycine/water.

Two-dimensional exchange spectroscopy revisited: Accounting for the number of participating spins