自组装的金属协调纳米螺旋作为高效和坚固的状超分子催化剂,用于酶选择性反应
Cong Gao1, Shixin Li2, Cici Zhao1
1School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu, 225002, China.
Small (Weinheim an der Bergstrasse, Germany)
|December 29, 2023
概括
从氨基酸两性和铜离子衍生出的基拉尔超分子催化剂在迪尔斯-阿尔德反应中表现出高的反选择性. 这些自组装的纳米结构,包括螺旋和带,使高效的不对称合成成为可能.
科学领域:
- 超分子化学 超分子化学
- 不对称的催化剂.
- 纳米材料是一种纳米材料.
背景情况:
- 开发性纳米结构用于具有高enantioselectivity的超分子催化是一种重大挑战.
- 氨基酸两类提供了一个有前途的构建模块,用于创建性超分子组件.
- 金属离子协调可以进一步增强这些自组装结构的催化性能.
研究的目的:
- 合成和研究基于氨基酸两和金属离子的性超分子催化剂.
- 系统地评估这些催化剂在不对称的迪尔斯-阿尔德反应中的酶选择性.
- 阐明结构-活性关系和调节对抗选择性结果的催化机制.
主要方法:
- 合成和各种氨基酸双胞胎的自我组装,特别是基于l/d-phenylglycine的双胞胎 (l/d-PhgC16).
- 与Cu (II) 离子的协调,在甲醇/水混合物中形成奇拉上分子催化剂.
- 自组装的纳米结构 (纳米螺旋和纳米丝带) 的表征和在迪尔斯-阿尔德反应中对异位选择性的评估.
- 性转移实验和分子动力学模拟以了解催化机制.
主要成果:
- 自组装的l/d-PhgC16和Cu(II) 产生了M/P纳米螺旋体 (≈8nm直径) 和纳米丝带.
- 由此产生的M/P超分子催化剂在迪尔斯-阿尔德反应中表现出高和反向的反反选择性 (>90% ee).
- 单质对应物显示出近乎racemic的产物,突出显示了超分子组合的重要性.
- 观察到从高分子结构到Cu (II) 和基质的性转移.
结论:
- 通过氨基酸两和金属离子的自我组装形成的状超分子催化剂可以实现高的反选择性.
- 超分子组件内的特定的立体化学微环境对于诱导酶选择性至关重要.
- 涉及性转移的拟议机制解释了在不对称的迪尔斯-阿尔德反应中观察到的酶选择性催化活性.
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