Chiral recognition of liquid phase dimers from gamma-valerolactone racemic mixture
Chiral recognition of liquid phase dimers from gamma-valerolactone racemic mixture
复制标题
γ-戊内酯外消旋混合物的液相二聚体的手性识别
DOI：
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发表时间：
2018
影响因子：
2.2
通讯作者：
L. C. Freitas
中科院分区：
文献类型：
--
作者：
F. Colombari;A. F. Moura;L. C. Freitas
γ-戊内酯（GVL）是一种环酯，由于其环保的物理和化学特性以及生物质生产成本低，可以被认为是化学过程中的绿色替代品。虽然GVL是一种手性溶剂，但它通常作为外消旋混合物使用，而不是纯手性形式，这可能会提高其在对映选择性合成和手性分离色谱技术中的性能。本报告介绍了通过蒙特卡罗 (MC) 和分子动力学 (MD) 模拟方法优化重现 GVL 液相特性的原子力场的开发和验证。优化的力场改进了对分子对之间相互作用的描述，这是正确评估 GVL 对映体形式之间微妙相互作用的关键方面。检查径向分布函数 (RDF) 以了解 GVL 外消旋混合物中发现的 RR、SS 和 RS 相互作用之间的相关性，结果显示第一个溶剂化壳层存在非常细微的差异。使用力场以及 HF-3c 和 PBEh-3c 量子化学方法分别计算了 RR、SS 和 RS 二聚体系综的平均相互作用能 EintRR$E_{int}^{RR}$、EintSS$E_{int}^{SS}$ 和 EintRS$E_{int}^{RS}$。对于每种方法，EintRR$E_{int}^{RR}$ 和 EintSS$E_{int}^{SS}$ 获得的结果值几乎相同，并且比 EintRS$E_{int}^{RS}$ 更负。此外，RR 和 SS 二聚体获得的平均能量波动高于 RS 获得的平均能量波动。
Gamma-valerolactone (GVL) is a cyclic ester that can be considered a green alternative in chemical processes due to its environmentally friendly physical and chemical properties and low production cost from biomass. Although GVL is a chiral solvent, it is usually used as a racemic mixture, instead of its homochiral forms, which might improve its performance in enantioselective synthesis and chiral separation chromatographic techniques. This report presents the development and validation of an atomistic force field optimized to reproduce GVL liquid-phase properties via Monte Carlo (MC) and molecular dynamics (MD) simulation methods. The optimized force field improved the description of the interactions between pairs of molecules, which is a key aspect for a proper assessment of subtle interactions between the enantiomeric forms of GVL. Inspection of radial distribution functions (RDF) for correlations between RR, SS, and RS interactions found within GVL racemic mixture shows very subtle differences at the first solvation shell. Average interaction energies EintRR$E_{int}^{RR}$, EintSS$E_{int}^{SS}$ and EintRS$E_{int}^{RS}$ for RR, SS, and RS dimer ensembles, respectively, were calculated with force field and also HF-3c and PBEh-3c quantum chemistry methods. For each methodology, resulting values obtained for EintRR$E_{int}^{RR}$ and EintSS$E_{int}^{SS}$ were almost the same and more negative than EintRS$E_{int}^{RS}$. Also, the average energy fluctuation obtained for RR and SS dimers were higher than the one obtained for RS.
影响因子：
5.5
作者：
Wang, Junmei;Hou, Tingjun
通讯作者：
Hou, Tingjun