Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an, 710069, P. R. China.
Shanghai Synchrotron Radiation Facility of Zhangjiang Lab, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204, P. R. China.
Angew Chem Int Ed Engl. 2021 Mar 15;60(12):6744-6751. doi: 10.1002/anie.202012681. Epub 2021 Feb 3.
Chiral framework materials have been developed for many applications including chiral recognition, chiral separation, asymmetric catalysis, and chiroptical materials. Herein, we report that an achiral cucurbit[8]uril-based supramolecular organic framework (SOF-1) with the dynamic rotational conformation of tetraphenylethene units can exhibit adaptive chirality to produce M-SOF-1 or P-SOF-1 with mirror-image circular dichroism (CD) with g ≈±10 and circularly polarized luminescence (CPL) with g ≈±10 induced by L-/D-phenylalanine in water, respectively. The chirality induction in CD (g ≈-10 ) and CPL (g ≈-10 ) of P-SOF-1 from achiral SOF-1 can be presented by using a small amount of adenosine-5'-triphosphate disodium (ATP) or adenosine-5'-diphosphate disodium (ADP) (only 0.4 equiv) in water. Furthermore, the adaptive chirality of SOF-1 can be used to determine dipeptide sequences (e.g., Phe-Ala and Ala-Phe) and distinguish polypeptides/proteins (e.g., somatostatin and human insulin) with characteristic CD spectra. Therefore, achiral SOF-1 as an ideal chiroptical platform with adaptive chirality may be applied to determine the enantiopurity of amino acids (e.g., L-/D-phenylalanine), develop aqueous CPL materials, and distinguish biological chiral macromolecules (e.g., peptides/proteins) via chirality induction in water.
手性框架材料已被开发用于许多应用，包括手性识别、手性分离、不对称催化和手性光学材料。在此，我们报告了一种基于葫芦[8]脲的超分子有机框架（SOF-1），其具有四苯乙烯单元的动态旋转构象，能够表现出自适应手性，以产生 M-SOF-1 或 P-SOF-1，它们具有镜像圆二色性（CD），g 值约为±10，圆偏振发光（CPL），g 值约为±10，分别由 L-/D-苯丙氨酸在水中诱导。在 CD（g ≈-10）和 CPL（g ≈-10）中，手性诱导来自于非手性 SOF-1 的 P-SOF-1，可以通过在水中使用少量的腺苷-5'-三磷酸二钠盐（ATP）或腺苷-5'-二磷酸二钠盐（ADP）（仅 0.4 当量）来实现。此外，SOF-1 的自适应手性可用于确定二肽序列（例如，Phe-Ala 和 Ala-Phe）并区分多肽/蛋白质（例如，生长抑素和人胰岛素），具有特征性的 CD 光谱。因此，非手性 SOF-1 作为具有自适应手性的理想手性光学平台，可能应用于确定氨基酸的对映体纯度（例如，L-/D-苯丙氨酸），开发水相 CPL 材料，并通过水相诱导区分生物手性大分子（例如，多肽/蛋白质）。
