DeSensi Susan C, Rangel David P, Beth Albert H, Lybrand Terry P, Hustedt Eric J
Department of Chemistry and Center for Structural Biology, Vanderbilt University, Nashville, Tennessee 37235, USA.
Biophys J. 2008 May 15;94(10):3798-809. doi: 10.1529/biophysj.107.125419. Epub 2008 Jan 30.
A simulated continuous wave electron paramagnetic resonance spectrum of a nitroxide spin label can be obtained from the Fourier transform of a free induction decay. It has been previously shown that the free induction decay can be calculated by solving the time-dependent stochastic Liouville equation for a set of Brownian trajectories defining the rotational dynamics of the label. In this work, a quaternion-based Monte Carlo algorithm has been developed to generate Brownian trajectories describing the global rotational diffusion of a spin-labeled protein. Also, molecular dynamics simulations of two spin-labeled mutants of T4 lysozyme, T4L F153R1, and T4L K65R1 have been used to generate trajectories describing the internal dynamics of the protein and the local dynamics of the spin-label side chain. Trajectories from the molecular dynamics simulations combined with trajectories describing the global rotational diffusion of the protein are used to account for all of the dynamics of a spin-labeled protein. Spectra calculated from these combined trajectories correspond well to the experimental spectra for the buried site T4L F153R1 and the helix surface site T4L K65R1. This work provides a framework to further explore the modeling of the dynamics of the spin-label side chain in the wide variety of labeling environments encountered in site-directed spin labeling studies.
可通过自由感应衰减的傅里叶变换获得氮氧自旋标记的模拟连续波电子顺磁共振谱。此前已表明,自由感应衰减可通过求解一组定义标记旋转动力学的布朗轨迹的含时随机刘维尔方程来计算。在这项工作中,已开发出一种基于四元数的蒙特卡罗算法,以生成描述自旋标记蛋白质全局旋转扩散的布朗轨迹。此外,T4溶菌酶的两个自旋标记突变体T4L F153R1和T4L K65R1的分子动力学模拟已用于生成描述蛋白质内部动力学和自旋标记侧链局部动力学的轨迹。将分子动力学模拟的轨迹与描述蛋白质全局旋转扩散的轨迹相结合,用于解释自旋标记蛋白质的所有动力学。从这些组合轨迹计算出的光谱与埋藏位点T4L F153R1和螺旋表面位点T4L K65R1的实验光谱非常吻合。这项工作提供了一个框架,以进一步探索在定点自旋标记研究中遇到的各种标记环境下自旋标记侧链动力学的建模。