Structural peculiarities of keto-carotenoids in water-soluble proteins revealed by simulation of linear absorption.
Structural peculiarities of keto-carotenoids in water-soluble proteins revealed by simulation of linear absorption.
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通过线性吸收模拟揭示水溶性蛋白质中酮类胡萝卜素的结构特性
DOI：
10.1039/c9cp04508b
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Maksimov
中科院分区：
文献类型：
--
作者：
Pishchalnikov;Yaroshevich;Slastnikova;Ashikhmin;Stepanov;Slutskaya;Friedrich;Sluchanko;Maksimov
为了防止由过量的入射光引起的不可逆的损伤，许多蓝细菌的光合机制独特地利用含有单个酮-类胡萝卜素分子的水溶性橙子类胡萝卜素蛋白（OCP）。该分子非共价嵌入通过柔性接头互连的两个OCP结构域中。OCP的光活化现象，引起显着的变化，类胡萝卜素的吸收在橙子和红色形式的OCP，目前正在深入研究。许多其他光谱形式的天然和合成的OCP样蛋白质已经被发掘出来。类胡萝卜素的光学性质强烈地由它们的电子状态与振动模式、周围蛋白质基质和溶剂的相互作用决定。本文通过线性吸收的计算模拟，研究了色素-蛋白质相互作用和振动弛豫对OCP的影响。考虑到拉曼光谱数据和应用多模布朗振子模型以及累积展开技术，我们已经计算了一组特征的微观参数足以划分不同的类胡萝卜素状态的OCP形式，使用模型类胡萝卜素spheroidene和spheroidone在甲醇/丙酮溶液作为基准。决定溶剂和蛋白质环境影响的最关键的微观参数是Huang-Rhys因子和CC和C-C伸缩模式的频率，低频模式和由于不均匀线加宽引起的FWHM。考虑到类胡萝卜素和类胡萝卜素酮之间的线性吸收的差异，这非常类似于光诱导的OCP吸收的变化，并应用量子化学计算，我们讨论了类胡萝卜素结合蛋白的结构和功能的决定因素。
To prevent irreversible damage caused by an excess of incident light, the photosynthetic machinery of many cyanobacteria uniquely utilizes the water-soluble orange carotenoid protein (OCP) containing a single keto-carotenoid molecule. This molecule is non-covalently embedded into the two OCP domains which are interconnected by a flexible linker. The phenomenon of OCP photoactivation, causing significant changes in carotenoid absorption in the orange and red form of OCP, is currently being thoroughly studied. Numerous additional spectral forms of natural and synthetic OCP-like proteins have been unearthed. The optical properties of carotenoids are strongly determined by the interaction of their electronic states with vibrational modes, the surrounding protein matrix, and the solvent. In this work, the effects of the pigment–protein interaction and vibrational relaxation in OCP were studied by computational simulation of linear absorption. Taking into account Raman spectroscopy data and applying the multimode Brownian oscillator model as well as the cumulant expansion technique, we have calculated a set of characteristic microparameters sufficient to demarcate different carotenoid states in OCP forms, using the model carotenoids spheroidene and spheroidenone in methanol/acetone solution as benchmarks. The most crucial microparameters, which determine the effect of solvent and protein environment, are the Huang–Rhys factors and the frequencies of CC and C–C stretching modes, the low-frequency mode and the FWHM due to inhomogeneous line broadening. Considering the difference of linear absorption between spheroidene and spheroidenone, which remarkably resembles the photoinduced changes of OCP absorption, and applying quantum chemical calculations, we discuss structural and functional determinants of carotenoid binding proteins.
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影响因子：
18.3
作者：
Polivka, Tomas;Frank, Harry A.
通讯作者：
Frank, Harry A.
橙色类胡萝卜素蛋白中3′-羟基海胆酮颜色变化的计算研究
影响因子：
2.8
作者：
Y. Mori
通讯作者：
Y. Mori
通过量子化学计算对环状类胡萝卜素在光合天线中的作用进行功能解释
DOI：
--
发表时间：
2015
期刊：
影响因子：
--
作者：
I. Yaroshevich;P. Krasilnikov;A. Rubin
通讯作者：
A. Rubin
来自沼泽红假单胞菌菌株的非典型可溶性血红素蛋白。
DOI：
--
发表时间：
1965
期刊：
Biochimica et Biophysica Acta
影响因子：
--
作者：
H. D. Klerk;R. G. Bartsch;Martin D. Kamen
通讯作者：
Martin D. Kamen
影响因子：
3.7
作者：
A. Moskalenko;Z. Makhneva;L. Fiedor;H. Scheer
通讯作者：
A. Moskalenko;Z. Makhneva;L. Fiedor;H. Scheer