Fazelpour Elham, Haseleu Jennifer M, Fennell Christopher J
Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078, United States.
School of Natural Sciences, Mathematics and Computing, St. Vincent College, Latrobe, Pennsylvania 15650, United States.
J Phys Chem B. 2025 Mar 6;129(9):2493-2504. doi: 10.1021/acs.jpcb.4c06069. Epub 2025 Feb 25.
Diffusion at the molecular level involves random collisions between particles, the structure of local microscopic environments, and interactions among the molecules involved. Sampling all of these aspects, along with correcting for finite-size effects, can make the calculation of infinitely dilute diffusion coefficients computationally difficult. We present a new approach for estimating the translational diffusion coefficient of biomolecular structures by encapsulating these driving forces of diffusion through piecewise assembly of the component residues of the protein structure. By linking the local chemistry of a solvent-exposed patch of a molecule to its contribution to the overall hydrodynamic radius, an accurate prediction of the computationally and experimentally comparable diffusion coefficients can be constructed following a solvent-excluded surface area calculation. We demonstrate that the resulting predictions for diffusion coefficients from peptides through to protein structures are comparable to explicit molecular simulations and improve on statistical mass-based predictions, which tend to rely on limited training data. As this approach uses the chemical identity of molecular structures, we find that it is able to predict and identify differences in diffusivity for structures that would be indistinguishable by mass information alone.
分子水平的扩散涉及粒子之间的随机碰撞、局部微观环境的结构以及相关分子之间的相互作用。对所有这些方面进行采样,并校正有限尺寸效应,会使无限稀释扩散系数的计算在计算上变得困难。我们提出了一种新方法,通过蛋白质结构组成残基的分段组装来封装这些扩散驱动力,从而估算生物分子结构的平移扩散系数。通过将分子暴露于溶剂的区域的局部化学性质与其对整体流体动力学半径的贡献联系起来,在计算溶剂排除表面积后,可以构建出在计算和实验上具有可比性的扩散系数的准确预测。我们证明,从肽到蛋白质结构的扩散系数的预测结果与显式分子模拟相当,并且优于基于统计质量的预测,后者往往依赖于有限的训练数据。由于这种方法使用分子结构的化学特性,我们发现它能够预测和识别仅通过质量信息无法区分的结构在扩散率上的差异。