Allenic retinals and visual pigment analogues

Nakanishi, K.; Yudd, Anthony P.; Crouch, R. K.; Olson, Gerry; Cheung, H.‐C.; Govindjee, Rajni; Ebrey, Thomas G.; Patel, D. J.

doi:10.1021/ja00417a040

Cited by 38 publications

(12 citation statements)

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“…A number of studies have shown that a variety of retinal analogues can be accommodated within the binding pocket in rhodopsin (24)(25)(26), which may help explain the existence of minor alternative structural forms in the current study. It was possible that a similar degree of structural heterogeneity with the chromophore could have interfered with the analysis of methyl orientations from the 2 H NMR measurements.…”

Section: Resultsmentioning

confidence: 75%

“…The structural flexibility noted within the binding pocket (24)(25)(26) has mainly been associated with the location of the ring segment. In the most recent work (26), it was concluded that even various conformations locked within the chain segment are accommodated, not by relocating the chain, but by cis to trans ring flips being allowed within the protein.…”

Section: Resultsmentioning

confidence: 99%

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Relative Orientation between the β-Ionone Ring and the Polyene Chain for the Chromophore of Rhodopsin in Native Membranes

et al. 2002

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Rotational resonance solid state nuclear magnetic resonance has been used to determine the relative orientation of the beta-ionone ring and the polyene chain of the chromophore 11-Z-retinylidene of rhodopsin in rod outer segment membranes from bovine retina. The bleached protein was regenerated with either 11-Z-[8,18-(13)C(2)]retinal or 11-Z-[8,16/17(13)C(2)]retinal, the latter having only one (13)C label at either of the chemically equivalent positions 16 and 17. Observation of (13)C selectively enriched in the ring methyl groups, C16/17, revealed alternative conformational states for the ring. Minor spectral components comprised around 26% of the chromophore. The major conformation (approximately 74%) has the chemical shift resolution required for measuring internuclear distances to (13)C in the retinal chain (C8) separately from each of these methyl groups. The resulting distance constraints, C8 to C16 and C17 (4.05 +/- 0.25 A) and from C8 to C18 (2.95 +/- 0.15 A), show that the major portion of retinylidene in rhodopsin has a twisted 6-s-cis conformation. The more precise distance measurement made here between C8 and C18 (2.95 A) predicts that the chain is twisted out-of-plane with respect to the ring by a modest amount (C5-C6-C7-C8 torsion angle = -28 +/- 7 degrees ).

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Section: Resultsmentioning

confidence: 75%

Section: Resultsmentioning

confidence: 99%

Relative Orientation between the β-Ionone Ring and the Polyene Chain for the Chromophore of Rhodopsin in Native Membranes

et al. 2002

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“…Of specific interest are the chromoproteins formed from allenic retinal and adamantyl-allenic retinal, which both have extensively altered cyclohexene rings [25,26]. The existence of these chromoproteins means that the binding space within opsin is able to accomodate different configurations of a cyclohexene ring.…”

Section: Discussionmentioning

confidence: 99%

Regeneration of Rhodopsin and Bacteriorhodopsin

Towner

Gaertner

Walckhoff

et al. 1981

European Journal of Biochemistry

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The rate of regeneration of rhodopsin, from I I-cis-retinal and opsin, and bacteriorhodopsin from all-transretinal and bacterio-opsin, in the presence or absence of compounds whose structures partially resemble retinal were measured. Some of these compounds severely slowed down the regeneration process, but did not influence the extent of regeneration. In the case of compounds with a carbonyl functional group they were not joined to the active site of the apo-protein via a Schiffs base linkage since after treatment with NaBH4 an active apo-protein remained. The most effective inhibitors of rhodopsin regeneration were molecules whose structure could be superimposed on 9 4 or 11-cis retinal up to carbon atom 11. These C13 and CIS molecules were not distinguished between aldehyde, ketone or alcohol functional groups.The regeneration of bacteriorhodopsin was not inhibited by retinal analogues with short side chains. The most effective inhibitors were the all-trans C1 d d e h y d e (j-ionylideneacetaldehyde) or c 1 8 -ketone (/I-ionylidenepent-3-ene-2-one) which, compared to retinal, lack two or three carbon atoms from the end of the polyene chain. The inhibition was very dependent upon the presence of the all-trans isomer and required aldehyde or ketone as functional group; nitriles and alcohols were less effective. However, similarly to retinol, the all-trans CI7 and c 1 8 alcohols underwent a bathochromic shift and showed fine-structured spectra when mixed with bacterio-opsin

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“…This restriction is in sharp contrast to the studies with the allenic retinoids that showed considerable leniency in the binding capabilities of the ionone binding site I. Thus, opsin could incorporate diastereomers 20, 21, and their respective enantiomers, 22 as well as the adamantyl retinoid 22.…”

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confidence: 78%

Synthesis of 11‐cis‐locked bicyclo[5.1.0]octanyl retinal and an enantioselective binding to bovine opsin

et al. 2002

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Both enantiomers of 13-(E) and 13-(Z) isomers of 11-cis-locked bicyclo[5.1.0]octanyl retinal were prepared by an improved synthesis and incubated with bovine opsin. The synthesis also establishes the absolute configuration of the enantiomers. Only one of the enantiomers binds to opsin, thus showing the steric restrictions regarding the middle polyene moiety of the retinoid molecule; this is in sharp contrast to the known leniency of the ring moiety binding site of retinoids. However, although one enantiomer is incorporated into the pigment, the circular dichroic spectrum of the pigment incorporating the bound enantiomer yields only a very weak Cotton effect, showing that, once incorporated, the bicyclo[5.1.0]octanyl chromophore is flattened by the opsin binding site. The titled retinoid was synthesized for study of the absolute conformation of the retinal pigment in rhodopsin.

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Allenic retinals and visual pigment analogues

Cited by 38 publications

References 0 publications

Relative Orientation between the β-Ionone Ring and the Polyene Chain for the Chromophore of Rhodopsin in Native Membranes

Relative Orientation between the β-Ionone Ring and the Polyene Chain for the Chromophore of Rhodopsin in Native Membranes

Regeneration of Rhodopsin and Bacteriorhodopsin

Synthesis of 11‐cis‐locked bicyclo[5.1.0]octanyl retinal and an enantioselective binding to bovine opsin

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