Separation of Enantiomers through Local Vorticity: A Screw Model Mechanism
Separation of Enantiomers through Local Vorticity: A Screw Model Mechanism
复制标题
通过局部涡度分离对映体：螺旋模型机制
DOI：
10.1021/acs.jpcb.1c07127
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Gezelter, J. Daniel
中科院分区：
文献类型：
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作者：
Duraes, Anderson D.;Gezelter, J. Daniel
我们提出了一个模型来解释流体中剪切流或局部旋转运动下对映体分离背后的机制。流体的局部涡旋会产生与平移运动耦合的分子旋转，从而向相反方向发送对映体。利用分子流体动力学阻力张量探索对映体的平移-旋转耦合，并引入螺杆螺距的分子当量来描述平移-旋转耦合的程度。分子间距是分子的结构特征，可以轻松计算，从而可以快速估计 85 种药物分子的间距。对一系列流体中的模型对映体进行模拟，例如水中的 Λ- 和 Δ-[Ru(bpy)3]Cl2 以及甲醇中的 (R,R)- 和 (S,S)-阿托伐他汀，支持使用分子螺距值进行的预测。开发了竞争模型和连续漂移扩散方程来预测实际外消旋混合物的分离。我们发现，利用实验上可实现的涡度，厘米长度尺度的对映体分离可以在数小时内实现。此外，我们发现某些非手性物体也可以表现出非零分子间距。
We present a model to explain the mechanism behind enantiomeric separation under either shear flow or local rotational motion in a fluid. Local vorticity of the fluid imparts molecular rotation that couples to translational motion, sending enantiomers in opposite directions. Translation–rotation coupling of enantiomers is explored using the molecular hydrodynamic resistance tensor, and a molecular equivalent of the pitch of a screw is introduced to describe the degree of translation–rotation coupling. Molecular pitch is a structural feature of the molecules and can be easily computed, allowing rapid estimation of the pitch of 85 druglike molecules. Simulations of model enantiomers in a range of fluids such as Λ- and Δ-[Ru(bpy)3]Cl2in water and (R,R)- and (S,S)-atorvastatin in methanol support predictions made using molecular pitch values. A competition model and continuum drift–diffusion equations are developed to predict separation of realistic racemic mixtures. We find that enantiomeric separation on a centimeter length scale can be achieved in hours, using experimentally achievable vorticities. Additionally, we find that certain achiral objects can also exhibit a nonzero molecular pitch.