Toward an understanding of the retinal chromophore in rhodopsin mimics

Mark M. Huntress, Samer Gozem, Konstantin R. Malley, Askat E. Jailaubekov, Chrysoula Vasileiou, Mikas Vengris, James H. Geiger, Babak Borhan, Igor Schapiro, Delmar S. Larsen, Massimo Olivucci*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

36 Scopus citations


Recently, a rhodopsin protein mimic was constructed by combining mutants of the cellular retinoic acid binding protein II (CRABPII) with an all-trans retinal chromophore. Here, we present a combined computational quantum mechanics/molecular mechanics (QM/MM) and experimental ultrafast kinetic study of CRABPII. We employ the QM/MM models to study the absorption (λamax), fluorescence (λf max), and reactivity of a CRABPII triple mutant incorporating the all-trans protonated chromophore (PSB-KLE-CRABPII). We also study the spectroscopy of the same mutant incorporating the unprotonated chromophore and of another double mutant incorporating the neutral unbound retinal molecule held inside the pocket. Finally, for PSB-KLE-CRABPII, stationary fluorescence spectroscopy and ultrafast transient absorption spectroscopy resolved two different evolving excited state populations which were computationally assigned to distinct locally excited and charge-transfer species. This last species is shown to evolve along reaction paths describing a facile isomerization of the biologically relevant 11-cis and 13-cis double bonds. This work represents a first exploratory attempt to model and study these artificial protein systems. It also indicates directions for improving the QM/MM models so that they could be more effectively used to assist the bottom-up design of genetically encodable probes and actuators employing the retinal chromophore.

Original languageAmerican English
Pages (from-to)10053-10070
Number of pages18
JournalJournal of Physical Chemistry B
Issue number35
StatePublished - 5 Sep 2013
Externally publishedYes


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