Corrections for off-resonance effects and incomplete saturation in conventional (two-site) saturation-transfer kinetic measurements
Abstract
The effects of off-resonance irradiation and incomplete saturation on saturation-transfer measurements of chemical-exchange rates are discussed. With off-resonance effects there is no exact formula for the exchange rate constant from spin D to spin E, kDE, in terms of observable signal intensities and relaxation rates. However, kDE can be estimated by measuring the effective spin-lattice relaxation rate constant of spin D when spin E is saturated, *R1, plus signal intensities with no RF irradiation, M0D and M0E; with irradiation of a control position, M′D and M′E; and with saturation of spin E, *MD and *ME. Several formulas are compared and the best formula for calculating kDE appears to be either kDE = *R1 [(M′D− *MD)/M0D]/[(M′E − *ME)/M0E], or the same formula with M0D and M0E replaced by M′D and M′E. These formulas are exact with incomplete saturation and no off-resonance effects, and are better than previously published formulas when off-resonance effects are present. More accurate formulas are available if signal intensities and relaxation rates can be measured while the exchange process is stopped. Magn Reson Med 43:810–819, 2000. © 2000 Wiley-Liss, Inc.