Tautomeric Forms of Metarhodopsin

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Abstract
Light isomerizes the chromophore of rhodopsin, 11-cis retinal (formerly retinene), to the all-trans configuration. This introduces a succession of unstable intermediates[long dash]pre-lumirhodopsin, lumirhodopsin, metarhodopsin[long dash]in which all-trans retinal is still attached to the chromophoric site on opsin. Finally, retinal is hydrolyzed from opsin. The present experiments show that metarhodopsin exists in two tautomeric forms, metarhodopsins I and II, with [lambda] max 478 and 380 m[mu]. Metarhodopsin I appears first, then enters into equilibrium with metarhodopsin n. In this equilibrium, the proportion of metarhodopsin II is favored by higher temperature or pH, neutral salts, and glycerol. The change from metarhodopsin I to II involves the binding of a proton by a group with pK 6.4 (imidazole?), and a large increase of entropy. Metarhodopsin II has been confused earlier with the final mixture of all-trans retinal and opsin ([lambda] max 387 m[mu]), which it resembles in spectrum. These two products are, however, readily distinguished experimentally.

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