Idrees Abdullah, Reuven Bar, Markovich Gil
School of Chemistry, Tel Aviv University, Tel Aviv 6997801, Israel.
J Am Chem Soc. 2025 Apr 30;147(17):14191-14197. doi: 10.1021/jacs.4c16883. Epub 2025 Apr 18.
The enantioselective adsorption (and catalysis) of molecules on chiral surfaces has been a topic of interest, in particular with respect to models describing homochirality in the evolution of life. While such adsorption on single crystal surfaces has been studied using various traditional surface science techniques, similar studies on powders have been less successful. Here we show that studying enantioselective adsorption on the particular system of intrinsically chiral TbPO·HO nanocrystals (chiral space group) is highly useful and obeys some simple rules. The advantages of this system are the ability to produce such nanocrystals with 100% enantiomeric purity with virtually no ligands, due to strong autocatalytic effects in their enantioselective nucleation, and the prevalence of one type of surface type (100) in the formed nanocrystals. We show that particular chiral molecules such as tartaric and aspartic acids exhibit significant enantioselectivity in adsorption, while similar ones, like glutamic acid, show none. We demonstrate that at least three functional groups are required to define enantioselective adsorption, and in addition, there should be matching of distances between these groups and the corresponding surface adsorption sites (Tb sites in our case).
分子在手性表面上的对映选择性吸附(以及催化作用)一直是一个备受关注的课题,特别是在描述生命演化中同手性的模型方面。虽然已经使用各种传统表面科学技术对单晶表面上的这种吸附进行了研究,但对粉末的类似研究却不太成功。在此我们表明,研究对映选择性吸附在本质上具有手性的TbPO·HO纳米晶体(手性空间群)这一特定体系上非常有用,并且遵循一些简单规则。该体系的优点在于,由于其对映选择性成核过程中的强自催化作用,能够在几乎没有配体的情况下制备出对映体纯度为100%的此类纳米晶体,并且在形成的纳米晶体中一种表面类型(100)占主导。我们表明,酒石酸和天冬氨酸等特定手性分子在吸附过程中表现出显著的对映选择性,而谷氨酸等类似分子则没有。我们证明,定义对映选择性吸附至少需要三个官能团,此外,这些基团与相应表面吸附位点(在我们的例子中是Tb位点)之间的距离应该匹配。