Compaction of single large dsDNA chains in aqueous solution in the presence
of primary alcohols, acetone, and ethylene glycol has been studied experim
entally with the use of a fluorescence microscopy technique. It is found th
at in the presence of all studied organic solvents single DNA molecules exh
ibit a discrete phase transition from an elongated coiled. to a compacted g
lobular conformation. interestingly, DNA phase transition occurred at vario
us weight fractions of organic solvents in aqueous solution, but at similar
dielectric constants of mixed solvent for all studied primary alcohols and
acetone. On the other hand, the dielectric constant of ethylene glycol-wat
er mixtures corresponding to the collapsing transition in single DNA differ
ed from that for the other studied systems. The explanation of this phenome
non comes through consideration of the existence of ethylene glycol conform
ers with various polarities in aqueous solution. Thus, the dielectric permi
ttivity of the solvent is a key factor that determines the conformational b
ehavior of DNA in solution. The compaction of a single DNA molecule when th
e dielectric permittivity constant is lowered is thought to be clue to the
increased importance of ion-ion correlation. Monte Carlo simulations for a
single polyelectrolyte chain also show that the dimensions of the chain dim
inish when the electrostatic coupling is increased, i.e., by decreasing the
dielectric constant. The experimental result can be rationalized with a si
mple free energy model balancing the counterion entropy and the ion-ion cor
relation energy.