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Temperature-dependent conformations of exciton-coupled Cy3 dimers in double-stranded DNA

机译:双链DNA中激子偶联Cy3二聚体的温度依赖性构型

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Understanding the properties of electronically interacting molecular chromophores, which involve internally coupled electronic-vibrational motions, is important to the spectroscopy of many biologically relevant systems. Here we apply linear absorption, circular dichroism, and two-dimensional fluorescence spectroscopy to study the polarized collective excitations of excitonically coupled cyanine dimers (Cy3)(2) that are rigidly positioned within the opposing sugar-phosphate backbones of the double-stranded region of a double-stranded (ds)-single-stranded (ss) DNA fork construct. We show that the exciton-coupling strength of the (Cy3)(2)-DNA construct can be systematically varied with temperature below the ds-ss DNA denaturation transition. We interpret spectroscopic measurements in terms of the Holstein vibronic dimer model, from which we obtain information about the local conformation of the (Cy3)(2) dimer, as well as the degree of static disorder experienced by the Cy3 monomer and the (Cy3)(2) dimer probe locally within their respective DNA duplex environments. The properties of the (Cy3)(2)-DNA construct we determine suggest that it may be employed as a useful model system to test fundamental concepts of protein-DNA interactions and the role of electronic-vibrational coherence in electronic energy migration within exciton-coupled bio-molecular arrays. Published by AIP Publishing.
机译:理解涉及内部耦合电子振动运动的电子相互作用的分子发色团的性质对许多生物相关系统的光谱很重要。在这里,我们应用线性吸收,圆形二中症和二维荧光光谱,以研究激谐偶联的花青二聚体(Cy3)(2)的极化集体激发,其刚性地定位在双链区域的相对的糖磷酸盐骨架内双链(DS) - 链股(SS)DNA叉构建体。我们表明(CY3)(2)-DNA构建体的激子耦合强度可以在低于DS-SS DNA变性转变的温度下系统地改变。我们根据荷斯坦振动二聚体模型来解释光谱测量,从中获得关于(CY3)(2)二聚体的局部构象的信息,以及Cy3单体和(Cy3)所经历的静态障碍程度(2)在其各自的DNA双链体环境中局部地探测器。 (2)-DNA构建体的性质我们确定它可以用作测试蛋白质-DNA相互作用的基本概念的有用模型系统,以及电子振动连贯在激子内的电子能量迁移中的作用 - 耦合生物分子阵列。通过AIP发布发布。

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