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一种模拟视觉色素并能在皮秒内完成其光循环的人工分子开关。

An artificial molecular switch that mimics the visual pigment and completes its photocycle in picoseconds.

作者信息

Sinicropi Adalgisa, Martin Elena, Ryazantsev Mikhail, Helbing Jan, Briand Julien, Sharma Divya, Léonard Jérémie, Haacke Stefan, Cannizzo Andrea, Chergui Majed, Zanirato Vinicio, Fusi Stefania, Santoro Fabrizio, Basosi Riccardo, Ferré Nicolas, Olivucci Massimo

机构信息

Dipartimento di Chimica, Università di Siena, via Aldo Moro 2, I-53100 Siena, Italy.

出版信息

Proc Natl Acad Sci U S A. 2008 Nov 18;105(46):17642-7. doi: 10.1073/pnas.0802376105. Epub 2008 Nov 11.

Abstract

Single molecules that act as light-energy transducers (e.g., converting the energy of a photon into atomic-level mechanical motion) are examples of minimal molecular devices. Here, we focus on a molecular switch designed by merging a conformationally locked diarylidene skeleton with a retinal-like Schiff base and capable of mimicking, in solution, different aspects of the transduction of the visual pigment Rhodopsin. Complementary ab initio multiconfigurational quantum chemistry-based computations and time-resolved spectroscopy are used to follow the light-induced isomerization of the switch in methanol. The results show that, similar to rhodopsin, the isomerization occurs on a 0.3-ps time scale and is followed by <10-ps cooling and solvation. The entire (2-photon-powered) switch cycle was traced by following the evolution of its infrared spectrum. These measurements indicate that a full cycle can be completed within 20 ps.

摘要

作为光能换能器的单分子(例如,将光子能量转化为原子级机械运动)是最小分子器件的示例。在这里,我们专注于一种分子开关,它通过将构象锁定的二芳叉骨架与视网膜样席夫碱合并设计而成,并且能够在溶液中模拟视觉色素视紫红质转导的不同方面。基于互补的从头算多组态量子化学计算和时间分辨光谱来跟踪该开关在甲醇中的光诱导异构化。结果表明,与视紫红质类似,异构化发生在0.3皮秒的时间尺度上,随后是小于10皮秒的冷却和溶剂化过程。通过跟踪其红外光谱的演变来追踪整个(双光子驱动的)开关循环。这些测量表明,一个完整的循环可以在20皮秒内完成。

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