Double-bond isomerization reactions in the retinoids provide a means t
o initiate and then to terminate signal transduction. An apt example i
s found in the visual system, where light causes the photoisomerizatio
n of the 11-cis-retinal protonated Schiff base of rhodopsin to its all
-trans congener. In order for vision to proceed, the reverse thermal i
somerization must take place. Because 11-cis-retinoids are approximate
ly 4 kcal/mol higher in energy than their all-trans counterparts, an e
nergy source is required for this conversion. It has been established
that the biosynthetic pathway for 11-cis-retinoids involves the direct
processing of all-trans retinyl esters to 11-cis-retinol. In this pro
cess, the negative free energy of ester hydrolysis provides the thermo
dynamic driving force for the endergonic trans to cis isomerization. S
ince retinyl esters are themselves generated by the transfer of acyl g
roups from phospholipids, the energy for the isomerization reaction or
iginates in the membrane phospholipids.