Department of Chemistry, Bowling Green State University, Bowling Green, OH 43403, USA.
Science. 2012 Sep 7;337(6099):1225-8. doi: 10.1126/science.1220461.
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 (λ(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 λ(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.
视网膜光感受器中的自发电信号对视觉灵敏度施加了限制。其起源归因于对转导级联的热激活,而不是光化学激活。尽管这种过程的机制存在争议,但对不同视觉色素的最大吸收波长(λ(max))和热激活动力学常数(k)之间关系的观察(Barlow 相关性)表明,热激活和光化学激活是相关的。在这里,我们表明牛视杆色素的量子化学模型提供了对 Barlow 相关性的分子水平理解。介导热激活的过渡态具有与光感受器激发态相同的电子结构,从而在 λ(max)和 k 之间建立了直接联系。这种联系似乎是与基态和激发态之间存在锥形交叉有关的固有发色团特征的表现。