2009
DOI: 10.1021/ja808424b
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Abstract: Hybrid QM(CASPT2//CASSCF/6-31G*)/MM(Amber) computations have been used to map the photoisomerization path of the retinal chromophore in Rhodopsin and explore the reasons behind the photoactivity efficiency and spectral control in the visual pigments. It is shown that while the electrostatic environment plays a central role in properly tuning the optical properties of the chromophore, it is also critical in biasing the ultrafast photochemical event: it controls the slope of the photoisomerization channel as wel… Show more

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Cited by 117 publications
(206 citation statements)
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References 73 publications
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“…Globally, the 27 residues in the cavity generate a blue shift of 10 kcal mol −1 , which results from large blue-shifting E113 effect contrasted by a cluster of residues creating a positive potential on the Schiff base region. This is consistent with the idea of a substantially "localized" counterion structure in Rh whose effect is partially quenched by the remaining opsin residues as also reported in previous studies using similar models (29,40,42).…”
Section: Significancesupporting
confidence: 92%
See 1 more Smart Citation
“…Globally, the 27 residues in the cavity generate a blue shift of 10 kcal mol −1 , which results from large blue-shifting E113 effect contrasted by a cluster of residues creating a positive potential on the Schiff base region. This is consistent with the idea of a substantially "localized" counterion structure in Rh whose effect is partially quenched by the remaining opsin residues as also reported in previous studies using similar models (29,40,42).…”
Section: Significancesupporting
confidence: 92%
“…As also observed in hMeOp and sqRh, nonpolar amino acids are mainly located around the β-ionone ring. In line with previous results (40)(41)(42)), the Rh model shows that the largest electrostatic effect is due to the putative E113 counterion (SI Appendix, Fig. S6).…”
Section: Significancesupporting
confidence: 91%
“…Most important, it delivers an accurate description of the photochemically relevant potential energy surfaces (PESs). The same protocol has been successfully coupled with the AMBER molecular mechanics force field to investigate the photoisomerization of the visual pigment rhodopsin (Rh) (4,36), returning energies that agree with the experiments. These studies support a two-state model for the retinal chromophore isomerization: the S 1 path develops entirely along a charge transfer (i.e., hole-pair 1B u -like) state and ends into a S 1 ∕S 0 conical intersection (CI) where the reacting double bond features a ca.…”
mentioning
confidence: 87%
“…The bR protein environment affects both the spectroscopic and photochemical properties of PSBT (2)(3)(4). First, the absorption maximum (568 nm) is red-shifted with respect to the one observed in solution (440 nm in methanol).…”
mentioning
confidence: 99%
“…E.g., the placement of the counter-ion to shift the absorption maximum will, uncorrected by the protein, lead to an avoided crossing situation instead of a conical intersection, which itself will reduce the quantum yield. 22 Still, the conversion in the protein pocket of Rh is ultrafast, unique and efficient. This is mainly achieved by shielding the electrostatic effects of the counterion that partially recovers the ideal in vacuo condition, 24,25 and by the pre-twisted conformation of retinal toward the photoproduct side, which allows for fast and stereoselective motion along the torsion coordinate, the out-of plane motions of carbon skeleton and their corresponding hydrogens being in line after photoexcitation.…”
mentioning
confidence: 99%