Photolysis intermediates of the artificial visual pigment cis-5,6-dihydro-isorhodopsin.
The photolysis intermediates of an artificial bovine rhodopsin pigment, cis-5,6-dihydro-isorhodopsin (cis-5,6,-diH-ISORHO, lambda max 461 nm), which contains a cis-5,6-dihydro-9-cis-retinal chromophore, are investigated by room temperature, nanosecond laser photolysis, and low temperature irradiation studies. The observations are discussed both in terms of low temperature experiments of Yoshizawa and co-workers on trans-5,6-diH-ISORHO (Yoshizawa, T., Y. Shichida, and S. Matuoka. 1984. Vision Res. 24: 1455-1463), and in relation to the photolysis intermediates of native bovine rhodopsin (RHO). It is suggested that in 5,6-diH-ISORHO, a primary bathorhodopsin intermediate analogous to the bathorhodopsin intermediate (BATHO) of the native pigment, rapidly converts to a blue-shifted intermediate (BSI, lambda max 430 nm) which is not observed after photolysis of native rhodopsin. The analogs from lumirhodopsin (LUMI) to meta-II rhodopsin (META-II) are generated subsequent to BSI, similar to their generation from BATHO in the native pigment. It is proposed that the retinal chromophore in the bathorhodopsin stage of 5,6-diH-ISORHO is relieved of strain induced by the primary cis to trans isomerization by undergoing a geometrical rearrangement of the retinal. Such a rearrangement, which leads to BSI, would not take place so rapidly in the native pigment due to ring-protein interactions. In the native pigment, the strain in BATHO would be relieved only on a longer time scale, via a process with a rate determined by protein relaxation.
Albeck
A
A
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel.
Friedman
N
N
Ottolenghi
M
M
Sheves
M
M
Einterz
C M
CM
Hug
S J
SJ
Lewis
J W
JW
Kliger
D S
DS
D007536:Isomerism; D010782:Photolysis; D012168:Retinal Pigments / Q000031:analogs & derivatives; D012243:Rhodopsin / Q000031:analogs & derivatives; D013053:Spectrophotometry; D013329:Structure-Activity Relationship
C059421:5,6-dihydroisorhodopsin; D012168:Retinal Pigments; D012243:Rhodopsin