基于共价有机框架的光酶纳米反应器,用于二次氨基的不对称动态动态动态分辨率
Lu Ran1, Yu Chen1, Yanqiu Zhu1
1College of Chemistry, Huazhong Agricultural University, Wuhan, 430070, P. R. China.
Angewandte Chemie (International ed. in English)
|February 17, 2024
概括
这项研究引入了一种新的光酶性纳米反应器,用于奇拉胺合成. CALB@COF-Ir系统增强了酶的稳定性,并使有效的非对称动态动力学分辨率成为可能,实现了高产量和选择性.
科学领域:
- 生物催化和纳米技术
- 有机合成 有机合成
- 光催化作用的光催化
背景情况:
- 自由酶的稳定性较差,反应范围有限,阻碍了工业应用.
- 胺胺是有价值的化合物,在药物和材料科学中广泛应用.
- 非对称的动态动力学分辨率 (DKR) 是合成enantiopure chiral amines的一个关键策略.
研究的目的:
- 开发一种稳定,高效的生物催化系统,用于合成奇拉胺.
- 克服工业生物催化剂中自由酶的局限性.
- 创建一个多功能纳米反应器,将酶活性与光催化相结合.
主要方法:
- 在光敏感共价有机框架 (COF-Ir) 中封装Candida antarctica脂酶B (CALB).
- 开发一个光酶纳米反应器 (CALB@COF-Ir) 以实现不对称的动态动力学分辨率 (DKR).
- 使用光诱导的原子转移 (HAT) 进行种族化和光电特性与TDDFT计算.
主要成果:
- CALB@COF-Ir纳米反应器有效催化了二次氨基的DKR,产生了高达99%的奇拉胺产量和99%的酶选择性.
- COF-Ir框架保护了CALB免于失活,并促进了氨酸的种族化.
- 通过促进电荷分离,COF-Ir内的 (ppy) 2Ir单位增强了光氧减氧特性.
- 不同质的纳米反应器在五个周期内表现出可回收性,活动损失最小.
结论:
- 开发的光酶纳米反应器CALB@COF-Ir提供了一个强大的平台,用于有效和立体选择性合成奇拉胺.
- 这种方法克服了酶的不稳定性,并通过综合光催化扩大了生物催化剂的范围.
- 可回收纳米反应器对价值的性化合物的可持续工业生产具有前景.
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