视觉色素的荧光量子产率：亚皮秒异构化速率的证据。
Fluorescence quantum yield of visual pigments: evidence for subpicosecond isomerization rates.
作者信息
Doukas A G, Junnarkar M R, Alfano R R, Callender R H, Kakitani T, Honig B
出版信息
Proc Natl Acad Sci U S A. 1984 Aug;81(15):4790-4. doi: 10.1073/pnas.81.15.4790.
Abstract
The fluorescence quantum yields (phi f) for bovine and squid rhodopsins are determined. Both pigments yield similar results, with an average value for phi f of 1.2 (+/- 0.5) X 10(-5). Since the estimated radiative lifetime of rhodopsin is 5 nsec, the rate constant of the process that competes with fluorescence must be on the order of 0.1 psec. Given the large quantum yield for isomerization of rhodopsin's retinal chromophore, this process is likely to correspond to the motion along retinal's C11-C12 torsional coordinate that leads to cis-trans isomerization. An empirical excited-state potential energy curve along this coordinate is derived. It is shown that subpicosecond torsional motion to highly twisted nonfluorescing regions of the potential is possible and, in fact, likely. Our results require the existence of a barrier-less excited-state potential energy curve and suggest that cis-trans isomerization occurs in less than 1 psec.
摘要
测定了牛视紫红质和鱿鱼视紫红质的荧光量子产率（φf）。两种色素产生的结果相似，φf的平均值为1.2（±0.5）×10⁻⁵。由于视紫红质的估计辐射寿命为5纳秒，与荧光竞争的过程的速率常数必须在0.1皮秒量级。鉴于视紫红质的视黄醛发色团异构化的量子产率很高，这个过程可能对应于沿着视黄醛的C11 - C12扭转坐标的运动，该运动导致顺反异构化。沿着这个坐标推导了一个经验性的激发态势能曲线。结果表明，亚皮秒级的扭转运动到势能的高度扭曲的非荧光区域是可能的，而且实际上很可能发生。我们的结果需要存在无势垒的激发态势能曲线，并表明顺反异构化在不到1皮秒的时间内发生。
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