Backbone Modification of Retinal Induces Protein-like Excited State Dynamics in Solution

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• 作者：Tina Sovdat ; Giovanni Bassolino ; Matz Liebel ; Christoph Schnedermann ; Stephen P. Fletcher ; Philipp Kukura
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：May 23, 2012
• 年：2012
• 卷：134
• 期：20
• 页码：8318-8320
• 全文大小：211K
• 年卷期：v.134,no.20(May 23, 2012)
• ISSN：1520-5126

文摘

The drastically different reactivity of the retinal chromophore in solution compared to the protein environment is poorly understood. Here, we show that the addition of a methyl group to the C鈺怌 backbone of all-trans retinal protonated Schiff base accelerates the electronic decay in solution making it comparable to the proton pump bacteriorhodopsin. Contrary to the notion that reaction speed and efficiency are linked, we observe a concomitant 50% reduction in the isomerization yield. Our results demonstrate that minimal synthetic engineering of potential energy surfaces based on theoretical predictions can induce drastic changes in electronic dynamics toward those observed in an evolution-optimized protein pocket.