The mercury(II) and high-salt-induced conformational B<==>Z transitions of poly[d(G-m5C).d(G-m5C)] as studied by non-polarized (ultraviolet) and circularly polarized (CD) ultraviolet spectroscopy.

The B<==>Z transition of poly[d(G-m5C).d(G-m5C)] in buffered solution (0.002 M sodium cacodylate, pH 7) was studied by CD and ultraviolet spectroscopy as a function of the supporting electrolyte concentration (0.002-1.1 M NaClO4) in the absence of Hg(ClO4)2 [Hg(II)], and as a function of the Hg(II) concentration at a given NaClO4 level. NaClO4 alone changes the conformation of the polymer from B<==>Z at approximately 0.7 M NaClO4. The spectral changes caused by Hg(II) in the B-form polymer (e.g. at 0.002 M < or = [Na] < or = 0.7) resemble those generated by salt alone during the B<==>Z transition; the changes generated by Hg(II) in the Z-form polymer (e.g. in 1.1 M [Na]) leave principally intact the Z-form spectrum obtained at the higher levels of NaClO4 (e.g. at [Na] > 0.7 M) in the absence of Hg(II). It is concluded that particularly the long-wavelength positive-CD band, located at 274 nm, is a correct indicator of duplex DNA right<==>left-screwness inversion. According to generally accepted criteria, the NaClO4-induced left-handed form is Z DNA; Hg(II) generates a left-handed form termed here ZHg(II). This form is close to (but not identical with) the salt-induced Z-form. All Hg(II)-induced spectral changes are reversible upon removal of Hg(II) with a suitable complexing reagent (e.g. NaCN).