title: Quantum mechanical/molecular mechanical structure, enantioselectivity, and spectroscopy of hydroxyretinals and insights into the evolution of color vision in small white butterflies.
abstract: Since Vogt's discovery of A(3)-retinal or 3-hydroxyretinal in insects in 1983 and Matsui's discovery of A(4)-retinal or 4-hydroxyretinal in firefly squid in 1988, hydroxyretinal-protein interactions mediating vision have remained largely unexplored. In the present study, A(3)- and A(4)-retinals are theoretically incorporated into squid and bovine visual pigments by use of the hybrid quantum mechanics/molecular mechanics [SORCI+Q//B3LYP/6-31G(d):Amber96] method, and insights into structure, enantioselectivity, and spectroscopy are gathered and presented for the first time. Contrary to general perception, our findings rule out the formation of a hydrogen bond between the hydroxyl-bearing β-ionone ring portion of retinal and opsin. Compared to A(1)-pigments, A(3)- and A(4)-pigments exhibit slightly blue-shifted absorption maxima due to increase in bond-length alternation of the hydroxyretinal. We suggest that (i) the binding site of firefly squid (Watasenia scintillans) opsin is very similar to that of the Japanese common squid (Todarodes pacificus) opsin; (ii) the molecular mechanism of spectral tuning in small white butterflies involve sites S116 and T185 and breaking of a hydrogen bond between sites E180 and T185; and finally (iii) A(3)-retinal may have occurred during the conversion of A(1)- to A(2)-retinal and insects may have acquired them, in order to absorb light in the blue-green wavelength region and to speed up the G-protein signaling cascade.
authors.affiliation: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA.
authors.forename: Sivakumar
authors.initials: S
authors.lastname: Sekharan
authors.forename: Shozo
authors.initials: S
authors.lastname: Yokoyama
authors.forename: Keiji
authors.initials: K
authors.lastname: Morokuma
mesh_terms: D019943:Amino Acid Substitution; D000818:Animals; D001665:Binding Sites; D002080:Butterflies / Q000737:chemistry / Q000378:metabolism; D002417:Cattle; D055253:Color Vision; D049832:Decapodiformes / Q000737:chemistry / Q000378:metabolism; D004224:Diterpenes; D008958:Models, Molecular; D055355:Opsins / Q000737:chemistry / Q000235:genetics / Q000378:metabolism; D017434:Protein Structure, Tertiary; D011789:Quantum Theory; D012172:Retinaldehyde / Q000031:analogs & derivatives* / Q000737:chemistry; D013053:Spectrophotometry; D013237:Stereoisomerism
chemical_list: D004224:Diterpenes; D055355:Opsins; C057180:4-hydroxyretinal; D012172:Retinaldehyde
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