Do you need a protein for efficient photochemistry?

您需要蛋白质来实现有效的光化学吗？

• 批准号: EP/K006630/1
• 负责人: Stephen Fletcher
• 金额: $ 85.29万
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2013
• 资助国家: 英国
• 起止时间: 2013 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FK006630%2F1
• 关键词: Do; need; protein; efficient; photochemistry

Some of the most essential processes in nature and for todays society and economy rely on the efficient interaction between light and matter. They range from photolithography used to create processors for todays computing needs to fundamental processes in nature, such as photosynthesis and vision. The latter exhibit a level of reactivity and speed that researchers have struggled for decades to recreate and understand in the laboratory. A case in point is the primary event in vision, the cis-trans isomerisation of the retinal chromophore in the visual pigment rhodopsin. This reaction is superbly fast and efficient when taking place inside the protein. 11-cis retinal in solution, however, reacts very slowly and inefficiently. The goal of our research is to unravel the source of the additional reactivity inside the protein. We have recently demonstrated for the first time, that a very minor chemical change to the retinal molecule can induce dynamics in solution that are comparable to those found in an evolution-optimised protein environment. The goal now is to systematically map the photochemical consequences of a series of potentially influential modifications to the molecule. The ultimate aim of this work is not only to reproduce the reactivity found in nature, but, more importantly, use the lessons learned in the design process to establish fundamental rules for what makes a light-induced process efficient and how it can be tuned rationally. These results will find applications in exactly those types of processes that have motivated the work in the first place: conversion of light into chemical energy for future alternative energy applications and the development of perfectly controllable molecular switches.

自然界以及当今社会和经济中一些最重要的过程依赖于光与物质之间的有效相互作用。它们的范围从用于创建满足当今计算需求的处理器的光刻到自然界的基本过程，例如光合作用和视觉。后者表现出一定程度的反应性和速度，研究人员几十年来一直在实验室中努力重现和理解。一个典型的例子是视觉中的主要事件，即视色素视紫红质中视网膜生色团的顺反异构化。当该反应在蛋白质内部发生时，速度非常快且非常高效。然而，溶液中的 11-顺式视黄醛反应非常缓慢且效率低下。我们研究的目标是揭示蛋白质内部额外反应性的来源。我们最近首次证明，视网膜分子的非常微小的化学变化可以在溶液中引起与进化优化的蛋白质环境中发现的动力学相当的动力学。现在的目标是系统地绘制一系列对该分子具有潜在影响的修饰的光化学后果。这项工作的最终目的不仅是重现自然界中发现的反应性，更重要的是，利用设计过程中吸取的经验教训，建立基本规则，使光诱导过程高效，以及如何合理调整它。这些结果将在最初推动这项工作的那些类型的过程中得到应用：将光转化为化学能，用于未来的替代能源应用，以及开发完全可控的分子开关。

项目成果

Barrierless Photoisomerization of 11-cis Retinal Protonated Schiff Base in Solution.

溶液中 11-顺式视网膜质子化席夫碱的无屏障光异构化。

• DOI: http://dx.10.1021/jacs.5b06492
• 发表时间: 2015
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Bassolino G

Wide-Field Detected Fourier Transform CARS Microscopy

宽视场检测傅立叶变换 CARS 显微镜

• DOI: 10.1038/srep37516
• 发表时间: 2016-11-24
• 期刊: Scientific Reports
• 影响因子: 4.6
• 作者: Duarte AS;Schnedermann C;Kukura P
• 通讯作者: Kukura P

Evidence for a vibrational phase-dependent isotope effect on the photochemistry of vision

振动相位依赖同位素对视觉光化学效应的证据

• DOI: 10.1038/s41557-018-0014-y
• 发表时间: 2018-03-19
• 期刊: Nature Chemistry
• 影响因子: 21.8
• 作者: C. Schnedermann;C. Schnedermann;Xuchun Yang;M. Liebel;K. Spillane;K. Spillane;K. Spillane;J. Lugtenburg;Isabelle Fernández Fernández;A. Valentini;A. Valentini;Igor Schapiro;M. Olivucci;M. Olivucci;M. Olivucci;Philipp Kukura;R. Mathies
• 通讯作者: R. Mathies

Synthetic control of retinal photochemistry and photophysics in solution.

溶液中视网膜光化学和光物理学的综合控制。

• DOI: http://dx.10.1021/ja4121814
• 发表时间: 2014
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Bassolino G

Wide-Field Detected Fourier Transform CARS Microscopy.

宽视场检测傅立叶变换 CARS 显微镜。

• DOI: http://dx.10.17863/cam.43276
• 发表时间: 2016
• 作者: Duarte A