Hypsochromic Shifts in Retinochrome Absorption Spectra in the Presence of Nitrate

The absorption wavelength of the protonated retinal Schiff base can be controlled by the surrounding environment. An external anion is related to fine adjustment of the absorption wavelength. The addition of anion to retinochrome solution caused blue shift in spectra. The increase of the shift was dependent on the ion concentration. The large shift value was obtained as 20 nm at the saturated concentration of nitrate. The shift intensity for the nitrate addition exceeded that of chloride. Seemingly, it depends on the ionic strength or lyotropic character of the anion. However, neither of sulphate nor gluconate ion showed remarkable blue shift. These phenomena were accounted for with (1) delocalization of the positive charge in the conjugated polyene system, (2) ionic bonding strength between the counter ion (glutamate) and the proton, and/or (3) interaction of the added anion with the proton on Schiff base.