The acid-base properties of the tetramine 1,5,10,14-tetraazatetradecane H2N(CH2)3NH(CH2)4NH(CH2)3NH2 (spermine) in deuterated water have been studied at 40 degrees C at various pD values by means of NMR spectroscopy. Both one-dimensional 13C[1H] spectra and two-dimensional 1H/13C heterocorrelation spectra with inverse detection have been recorded. A calculation procedure of general validity has been developed to unravel the effect of rapid exchange between the various species in equilibrium as a function of pD of the solution. The method of calculation used in this part of the new computer program, HYPNMR, is independent of the equilibrium model. HYPNMR has been used to obtain the basicity constants of spermine with respect to the D+ cation at 40 degrees C. Calculations have been performed using either 13C[1H] or 1H/13C data individually, or using both sets of data simultaneously. The results of the latter calculations were practically the same as the results obtained with the single data sets; the calculated errors on the refined parameters were a little smaller. After appropriate empirical corrections for temperature effects and for the presence of D+ in contrast to H+, the calculated constants are compared with spermine protonation constants which have been determined previously both from potentiometric and NMR data.