Probing the remarkable thermal kinetics of visual rhodopsin with E181Q and S186A mutants

Guo, Ying; Hendrickson, Heidi P.; Videla, Pablo E.; Chen, Ya-Na; Ho, Junming; Sekharan, Sivakumar; Batista, Victor S.; Tully, John C.; Yan, Elsa C.  Y.

doi:10.1063/1.4984818

Title: Probing the remarkable thermal kinetics of visual rhodopsin with E181Q and S186A mutants

Journal Article · Wed Jun 07 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4984818· OSTI ID:1474078

Guo, Ying ^[1];

^[1]; Videla, Pablo E. ^[1]; Chen, Ya-Na ^[1]; Ho, Junming ^[1]; Sekharan, Sivakumar ^[1]; Batista, Victor S. ^[1]; Tully, John C. ^[1]; Yan, Elsa C. Y. ^[1]

Yale Univ., New Haven, CT (United States). Dept. of Chemistry

We recently reported a very unusual temperature dependence of the rate of thermal reaction of wild type bovine rhodopsin: the Arrhenius plot exhibits a sharp “elbow” at 47 °C and, in the upper temperature range, an unexpectedly large activation energy (114 ± 8 kcal/mol) and an enormous prefactor (10^72±5 s^-1). In this report, we present new measurements and a theoretical model that establish convincingly that this behavior results from a collective, entropy-driven breakup of the rigid hydrogen bonding networks (HBNs) that hinder the reaction at lower temperatures. For E181Q and S186A, two rhodopsin mutants that disrupt the HBNs near the binding pocket of the 11-cis retinyl chromophore, we observe significant decreases in the activation energy (~90 kcal/mol) and prefactor (~10⁶⁰ s^-1), consistent with the conclusion that the reaction rate is enhanced by breakup of the HBN. Finally, the results provide insights into the molecular mechanism of dim-light vision and eye diseases caused by inherited mutations in the rhodopsin gene that perturb the HBNs.

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Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: FG02-05ER15677; MCB-0955407; CHE 1465108

OSTI ID:: 1474078

Alternate ID(s):: OSTI ID: 1365428

Journal Information:: Journal of Chemical Physics, Vol. 146, Issue 21; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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