  By equilibrating condensed DNA arrays against reservoirs of known osmotic
stress and examining them with several structural probes, it has been possible
to achieve a detailed thermodynamic and structural characterization of the
change between two distinct regions on the liquid crystalline phase digram: a
higher-density hexagonally packed region with long-range bond orientational
order in the plane perpendicular to the average molecular direction; and a
lower-density cholesteric region with fluid-like positional order. X-rays
scattering on highly ordered DNA arrays at high density and with the helical
axis oriented parallel to the incoming beam showed a six-fold azimuthal
modulation of the first order diffraction peak that reflects the macroscopic
bond-orientational order. Transition to the less-dense cholesteric phase
through osmotically controlled swelling shows the loss of this bond
orientational order that had been expected from the change in optical
birefringence patterns and that is consistent with a rapid onset of molecular
positional disorder. This change in motion was previously inferred from
intermolecular force measurements and is now confirmed by $\rm ^{31}P$ NMR.
Controlled reversible swelling and compaction under osmotic stress, spanning a
range of densities between $\sim 120$ mg/ml to $\sim 600$ mg/ml, allows
measurement of the free energy changes throughout each phase and at the phase
transition, essential information for theories of liquid-crystalline states.
