Motoori Junnosuke, Kinoshita Tomokazu, Chai Hongxin, Li Ming-Shuang, Wang Song-Meng, Jiang Wei, Fukuhara Gaku
Department of Chemistry, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
Shenzhen Xinhua Middle School, Shenzhen 518109, China.
ACS Nanosci Au. 2024 Oct 21;4(6):435-442. doi: 10.1021/acsnanoscienceau.4c00052. eCollection 2024 Dec 18.
The dynamic control of chiral (enantiomeric) responses in chiral host-guest complexes through external stimuli is a significant challenge in modern chemistry for developing smart stimuli-responsive materials. Herein, we report the (chir)optical properties and chiral recognition behavior of water-soluble chiral naphthotubes () under the influence of hydrostatic pressure as an external stimulus. The hydrostatic pressure spectral profiles compared to those obtained at normal pressure revealed the dynamic behavior of under hydrostatic pressure, owing to the flexible linker. In chiral recognition experiments, hydrophilic amino acids such as phenylalanine (Phe) and tryptophan (Trp) exhibited reaction volume changes (Δ°) of -0.9 cm mol for d-Phe, -1.2 cm mol for l-Phe, -5.6 cm mol for d-Trp, and -7.0 cm mol for l-Trp, with enantioselectivity ranging from 1.2 to 1.6. In contrast, hydrophobic chiral styrene oxide () showed Δ° values of 1.5 cm mol for - and 3.5 cm mol for , with a relatively higher enantioselectivity of up to 7.6. These contrasting effects of hydrostatic pressure primarily originate from the dynamics of chiral naphthotubes.
通过外部刺激对手性主客体复合物中的手性（对映体）响应进行动态控制，是现代化学中开发智能刺激响应材料的一项重大挑战。在此，我们报道了作为外部刺激的静水压力影响下，水溶性手性萘管（）的（手性）光学性质和手性识别行为。与常压下获得的光谱轮廓相比，静水压力光谱轮廓揭示了由于柔性连接体，在手性萘管在静水压力下的动态行为。在手性识别实验中，亲水性氨基酸如苯丙氨酸（Phe）和色氨酸（Trp），对于d-Phe的反应体积变化（Δ°）为-0.9 cm³/mol，对于l-Phe为-1.2 cm³/mol，对于d-Trp为-5.6 cm³/mol，对于l-Trp为-7.0 cm³/mol，对映选择性范围为1.2至1.6。相比之下，疏水性手性氧化苯乙烯（）对于-的Δ°值为1.5 cm³/mol，对于的为3.5 cm³/mol，对映选择性相对较高，高达7.6。静水压力的这些对比效应主要源于手性萘管的动力学。
