All-trans- and 11-cis-retinal, their N-methyl Schiff base and N-methyl protonated Schiff base derivatives: a comparative ab initio study

Terstegen, Frank; Buß, Volker

doi:10.1016/s0166-1280(96)04559-9

Cited by 25 publications

(14 citation statements)

References 57 publications

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“…The x-ray model and rotational resonance solid-state MAS NMR studies demonstrate that the C5-C8 segment has a twisted out-of-plane conformation (3,4,54). Ab initio calculations on pSB models suggested that the C5AC6 bond and the adjacent methyl group C-18 lie in one plane (42). Conformational distortions might be the origin of the observed small ⌬˜l ig C for C-5 and C18.…”

Section: Nmr Ligation Shifts In the Ionone Moiety Of The Chromophore mentioning

confidence: 92%

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¹ H and ¹³ C MAS NMR evidence for pronounced ligand–protein interactions involving the ionone ring of the retinylidene chromophore in rhodopsin

Creemers

Kiihne

Bovée-Geurts

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

120

184

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Rhodopsin is a member of the superfamily of G-protein-coupled receptors. This seven ␣-helix transmembrane protein is the visual pigment of the vertebrate rod photoreceptor cells that mediate dim light vision. In the active binding site of this protein the ligand or chromophore, 11-cis-retinal, is covalently bound via a protonated Schiff base to lysine residue 296. Here we present the complete 1 H and 13 C assignments of the 11-cis-retinylidene chromophore in its ligand-binding site determined with ultra high field magic angle spinning NMR. Native bovine opsin was regenerated with 99% enriched uniformly 13 C-labeled 11-cis-retinal. From the labeled pigment, 13 C carbon chemical shifts could be obtained by using two-dimensional radio frequency-driven dipolar recoupling in a solid-state magic angle spinning homonuclear correlation experiment.

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Section: Nmr Ligation Shifts In the Ionone Moiety Of The Chromophore mentioning

confidence: 92%

“…Because the 12-s-cis conformation is energetically favorable over the 12-s-trans, the equilibrium will be shifted in solution toward 12-s-cis (Fig. 1B) (42). In the protein, however, there is a nonplanar 12-s-trans conformation ( Fig.…”

Section: Charge Delocalization In the Polyene Chain Of The 11-cis-retmentioning

confidence: 99%

¹ H and ¹³ C MAS NMR evidence for pronounced ligand–protein interactions involving the ionone ring of the retinylidene chromophore in rhodopsin

Creemers

Kiihne

Bovée-Geurts

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

120

184

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“…We therefore resorted to MP2 and its analytical gradients, which allow for an efficient geometry search with a correlated wave function. Starting with the DFT-optimized structures (18), the chromophores were reoptimized with MP2 using a 6-31G** basis set (19).…”

mentioning

confidence: 99%

Ground and Excited States of Retinal Schiff Base Chromophores by Multiconfigurational Perturbation Theory

Sekharan

Weingart

Buß

2006

Biophysical Journal

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We have studied the wavelength dependence of retinal Schiff base absorbencies on the protonation state of the chromophore at the multiconfigurational level of theory using second order perturbation theory (CASPT2) within an atomic natural orbital basis set on MP2 optimized geometries. Quantitative agreement between calculated and experimental absorption maxima was obtained for protonated and deprotonated Schiff bases of all-trans- and 11-cis-retinal and intermediate states covering a wavelength range from 610 to 353 nm. These data will be useful as reference points for the calibration of more approximate schemes.

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“…A brief discussion regarding the characteristic features of the C6–C7 dihedral angle may be required. Until date, various theoretical methods have been used for the retinal structure in vacuo 11 , 27 , 40 , 49 – 50 . Notably, all of these supported non-planar conformers for both 6-s- trans and 6-s- cis forms, where steric hindrance occurred between methyl groups bound to the C1 or C5 atom and polyene branch.…”

Section: Resultsmentioning

confidence: 99%

Molecular mechanism of long-range synergetic color tuning between multiple amino acid residues in conger rhodopsin

et al. 2010

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The synergetic effects of multiple rhodopsin mutations on color tuning need to be completely elucidated. Systematic genetic studies and spectroscopy have demonstrated an interesting example of synergetic color tuning between two amino acid residues in conger rhodopsin’s ancestral pigment (p501): — a double mutation at one nearby and one distant residue led to a significant λmax blue shift of 13 nm, whereas neither of the single mutations at these two sites led to meaningful shifts.To analyze the molecular mechanisms of this synergetic color tuning, we performed homology modeling, molecular simulations, and electronic state calculations. For the double mutant, N195A/A292S, in silico mutation analysis demonstrated conspicuous structural changes in the retinal chromophore, whereas that of the single mutant, A292S, was almost unchanged. Using statistical ensembles of QM/MM optimized structures, the excitation energy of retinal chromophore was evaluated for the three visual pigments. As a result, the λmax shift of double mutant (DM) from p501 was −8 nm, while that of single mutant (SM) from p501 was +1 nm. Molecular dynamics simulation for DM demonstrated frequent isomerization between 6-s-cis and 6-s-trans conformers. Unexpectedly, however, the two conformers exhibited almost identical excitation energy, whereas principal component analysis (PCA) identified the retinal-counterion cooperative change of BLA (bond length alternation) and retinal-counterion interaction lead to the shift.

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All-trans- and 11-cis-retinal, their N-methyl Schiff base and N-methyl protonated Schiff base derivatives: a comparative ab initio study

Cited by 25 publications

References 57 publications

¹ H and ¹³ C MAS NMR evidence for pronounced ligand–protein interactions involving the ionone ring of the retinylidene chromophore in rhodopsin

¹ H and ¹³ C MAS NMR evidence for pronounced ligand–protein interactions involving the ionone ring of the retinylidene chromophore in rhodopsin

Ground and Excited States of Retinal Schiff Base Chromophores by Multiconfigurational Perturbation Theory

Molecular mechanism of long-range synergetic color tuning between multiple amino acid residues in conger rhodopsin

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All-trans- and 11-cis-retinal, their N-methyl Schiff base and N-methyl protonated Schiff base derivatives: a comparative ab initio study

Cited by 25 publications

References 57 publications

1 H and 13 C MAS NMR evidence for pronounced ligand–protein interactions involving the ionone ring of the retinylidene chromophore in rhodopsin

1 H and 13 C MAS NMR evidence for pronounced ligand–protein interactions involving the ionone ring of the retinylidene chromophore in rhodopsin

Ground and Excited States of Retinal Schiff Base Chromophores by Multiconfigurational Perturbation Theory

Molecular mechanism of long-range synergetic color tuning between multiple amino acid residues in conger rhodopsin

Contact Info

Product

Resources

About

¹ H and ¹³ C MAS NMR evidence for pronounced ligand–protein interactions involving the ionone ring of the retinylidene chromophore in rhodopsin

¹ H and ¹³ C MAS NMR evidence for pronounced ligand–protein interactions involving the ionone ring of the retinylidene chromophore in rhodopsin