Photochemical reactions of 13-demethyl visual pigment analogues at low temperatures.

The photobleaching reaction of 13-demethylisorhodopsin (hereafter designated as 9-cis- 13-dm-rhodopsin), which was synthesized from 9-cis- 13-demethylretinal and cattle opsin, was investigated by low-temperature spectrophotometry in order to elucidate the role of the 13-methyl group of retinal in photobleaching. When 9-cis- 13-dm-rhodopsin was irradiated at-190 degrees C, batho-13-dm-rhodopsin was produced. Its absorption maximum lay at 532 nm, 11 nm shorter than that of cattle bathorhodopsin (gamma max 543 nm), and batho-13-dm-rhodopsin had an extinction coefficient about 0.6 times that of bathorhodopsin. Batho-13-dm-rhodopsin was thermally unstable. Above-180 degrees C, it converted to a new intermediate, BL-13-dm-rhodopsin, which in turn changed to lumi-13-dm-rhodopsin- above -140 degrees C. BL-13-dm-rhodopsin was "photosensitive" at temperatures around -188 degrees C, though batho-13-dm-rhodopsin and lumi-13-dm-rhodopsin was "photosensitive" at the same temperature. In the photobleaching process, lumi-13-dm-rhodopsin and meta-I-13-dm-rhodopsin were observed. Their thermostabilities were very similar to those of lumirhodopsin and metarhodopsin I, but each dm intermediate differed from its methylated counterpart in its value of gamma max and extinction coefficient.