The effect of different organic osmolytes on the DNA counterion conden
sation layer has been investigated by Na-23 NMR relaxation measurement
s. The zwitterionic compounds glycine, beta-alanine, 4-aminobutyric ac
id, and 6-aminocaproic acid have shown an increasing capacity to decre
ase the amount of sodium ions in the vicinity of the macromolecule. Th
e experimental data have been correlated with the dielectric constant
increase in their corresponding solutions and have been compared with
the prediction of counterion condensation theory. Polyols (sorbitol an
d mannitol) did not display the same effect. These compounds largely i
ncrease the relaxation rate of sodium ions in the proximity of DNA, un
like the zwitterionic compounds. This probably results from a perturba
tion of the water dynamic around the macromolecule, of the primary or
secondary hydration shell of the sodium nuclei involved, or both.