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在手性中熵陶瓷上的对映选择性吸附

Enantioselective adsorption on chiral ceramics with medium entropy.

作者信息

Chen Chao, Ma Yinglin, Yao Kunda, Ji Qingmin, Liu Wei

机构信息

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China.

Herbert Gleiter Institute for Nanoscience, Nanjing University of Science and Technology, 200 Xiaolingwei, Nanjing, Jiangsu, China.

出版信息

Nat Commun. 2024 Nov 21;15(1):10105. doi: 10.1038/s41467-024-54414-8.

Abstract

Chiral metal surfaces provide an environment for enantioselective adsorption in various processes such as asymmetric catalysis, chiral recognition, and separation. However, they often suffer from limitations such as reduced enantioselectivity caused by kink coalescence and atomic roughness. Here, we present an approach using medium-entropy ceramic (MEC), specifically (CrMoTa)Si with a C40 hexagonal crystal structure, which overcomes the trade-off between thermal stability and enantioselectivity. Experimental confirmation is provided by employing quartz crystal microbalance (QCM), where the electrode is coated with MEC films using non-reactive magnetron sputtering technology. The chiral nature is verified through transmission electron microscopy and circular dichroism. Density-functional theory (DFT) calculations show that the stability of MEC films is significantly higher than that of high-index Cu surfaces. Through a combination of high-throughput DFT calculations and theoretical modeling, we demonstrate the high enantioselectivity (42% e.e.) of the chiral MEC for serine, a prototype molecule for studying enantioselective adsorption. The QCM results show that the adsorption amount of L-serine is 1.58 times higher than that of D-serine within a concentration range of 0-60 mM. These findings demonstrate the potential application of MECs in chiral recognition.

摘要

手性金属表面为不对称催化、手性识别和分离等各种过程中的对映选择性吸附提供了一个环境。然而,它们常常受到诸如扭结聚结和原子粗糙度导致的对映选择性降低等限制。在此,我们提出一种使用中熵陶瓷(MEC)的方法,具体为具有C40六方晶体结构的(CrMoTa)Si,它克服了热稳定性和对映选择性之间的权衡。通过采用石英晶体微天平(QCM)提供了实验证实,其中使用非反应磁控溅射技术在电极上涂覆MEC薄膜。通过透射电子显微镜和圆二色性验证了其手性性质。密度泛函理论(DFT)计算表明,MEC薄膜的稳定性明显高于高指数Cu表面。通过高通量DFT计算和理论建模相结合,我们证明了手性MEC对丝氨酸(一种用于研究对映选择性吸附的原型分子)具有高对映选择性(42% 对映体过量)。QCM结果表明,在0 - 60 mM的浓度范围内,L - 丝氨酸的吸附量比D - 丝氨酸高1.58倍。这些发现证明了MEC在 chiral recognition中的潜在应用。 (注:原文中“chiral recognition”未翻译,可能是笔误,推测应为“手性识别”)

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf6f/11582819/e82083a975a0/41467_2024_54414_Fig1_HTML.jpg

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