The Molecular Mechanism of Thermal Noise in Rod Photoreceptors

被引:91
作者
Gozem, Samer [1 ]
Schapiro, Igor [1 ]
Ferre, Nicolas [2 ]
Olivucci, Massimo [1 ,3 ]
机构
[1] Bowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
[2] Univ Aix Marseille, Inst Chim Radicalaire, UMR 7273, F-13397 Marseille 20, France
[3] Univ Siena, Dipartimento Chim, I-53100 Siena, Italy
关键词
POTENTIAL-ENERGY SURFACES; VISUAL PIGMENTS; CONICAL INTERSECTION; RHODOPSIN; ISOMERIZATION; VISION; ACTIVATION; DARK; PHOTOISOMERIZATION; PHOTOACTIVATION;
D O I
10.1126/science.1220461
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Spontaneous electrical signals in the retina's photoreceptors impose a limit on visual sensitivity. Their origin is attributed to a thermal, rather than photochemical, activation of the transduction cascade. Although the mechanism of such a process is under debate, the observation of a relationship between the maximum absorption wavelength (lambda(max)) and the thermal activation kinetic constant (k) of different visual pigments (the Barlow correlation) indicates that the thermal and photochemical activations are related. Here we show that a quantum chemical model of the bovine rod pigment provides a molecular-level understanding of the Barlow correlation. The transition state mediating thermal activation has the same electronic structure as the photoreceptor excited state, thus creating a direct link between lambda(max) and k. Such a link appears to be the manifestation of intrinsic chromophore features associated with the existence of a conical intersection between its ground and excited states.
引用
收藏
页码:1225 / 1228
页数:4
相关论文
共 30 条
[1]   On the relation between the photoactivation energy and the absorbance spectrum of visual pigments [J].
Ala-Laurila, P ;
Pahlberg, J ;
Koskelainen, A ;
Donner, K .
VISION RESEARCH, 2004, 44 (18) :2153-2158
[2]   Thermal activation and photoactivation of visual pigments [J].
Ala-Laurila, P ;
Donner, K ;
Koskelainen, A .
BIOPHYSICAL JOURNAL, 2004, 86 (06) :3653-3662
[3]   Structure, initial excited-state relaxation, and energy storage of rhodopsin resolved at the multiconfigurational perturbation theory level [J].
Andruniów, T ;
Ferré, N ;
Olivucci, M .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2004, 101 (52) :17908-17913
[4]   POTENTIAL-ENERGY SURFACES NEAR INTERSECTIONS [J].
ATCHITY, GJ ;
XANTHEAS, SS ;
RUEDENBERG, K .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (03) :1862-1876
[5]   PURKINJE SHIFT AND RETINAL NOISE [J].
BARLOW, HB .
NATURE, 1957, 179 (4553) :255-256
[6]   ON THE MOLECULAR-ORIGIN OF PHOTORECEPTOR NOISE [J].
BARLOW, RB ;
BIRGE, RR ;
KAPLAN, E ;
TALLENT, JR .
NATURE, 1993, 366 (6450) :64-66
[7]   2 COMPONENTS OF ELECTRICAL DARK NOISE IN TOAD RETINAL ROD OUTER SEGMENTS [J].
BAYLOR, DA ;
MATTHEWS, G ;
YAU, KW .
JOURNAL OF PHYSIOLOGY-LONDON, 1980, 309 (DEC) :591-621
[8]   Retinal phosphenes and discrete dark noises in rods: A new biophysical framework [J].
Bokkon, Istvan ;
Vimal, Ram Lakhan Pandey .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY, 2009, 96 (03) :255-259
[9]   Characterization of the conical intersection of the visual pigment rhodopsin at the CASPT2//CASSCF/AMBER level of theory [J].
Coto, PB ;
Sinicropi, A ;
De Vico, L ;
Ferré, N ;
Olivucci, M .
MOLECULAR PHYSICS, 2006, 104 (5-7) :983-991
[10]   New general tools for constrained geometry optimizations [J].
De Vico, L ;
Olivucci, M ;
Lindh, R .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2005, 1 (05) :1029-1037