Beijing National Laboratory of Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, No. 2 Zhongguancun, Beiyijie, Beijing, 100190, P. R. China.
School of Chemical Sciences, University of Chinese Academy of Sciences, 19 A Yuquanlu, Beijing, 100049, P. R. China.
Chem Asian J. 2023 Jun 15;18(12):e202300285. doi: 10.1002/asia.202300285. Epub 2023 May 15.
Enzymatic cascade reactions in confined microenvironments play important roles in cellular chemical transformation. Controlling enzymatic efficiency and eliminating substrate interference in cascade reactions is of great significance. To this end, a vesicle composed of poly(styrene-maleic anhydride-N-isopropylacrylamide)(P(S-M-NIP)) and functionalized with 1,2-bis(10,12- tricosadiynoyl)-sn-glycero-3-phosphocholine (DC PC) was designed herein. Based on the thermo-sensitive property of P(S-M-NIP) and the photo-responsive property of DC PC, a serial of dual-stimuli-responsive nanoreactors was constructed via enzymes encapsulation to tune their enzymolysis efficiencies. A kinetics study of the glucose oxidase-encapsulated nanoreactor indicated that its enzymolysis velocity increased 2.1- and 1.6-fold under heating and the ultraviolet (UV)-light irradiation, respectively. Consequently, an enzymatic cascade reaction in the proposed enzyme reactor encapsulated with β-galactosidase and glucose oxidase was investigated. The results revealed a 2.9-fold enhancement in enzymolysis efficiency by changing the ambient temperature under UV irradiation. The dual-stimuli-responsive polymer vesicles could also eliminate H O interference during the enzymatic cascade reaction. The vesicles demonstrated potential for switch-membrane-permeability, while, the confined microenvironment played a key role in regulating the reactions upon the temperature change and the presence of UV light. Our synthetic multi-organelle-like system provides a new way to mimic the control of cascade reaction catalytic processes by programming the "open/close" sates of the nanocapsules.
在受限的微环境中，酶级联反应在细胞化学转化中起着重要作用。控制级联反应中的酶效率和消除底物干扰具有重要意义。为此，设计了一种由聚（苯乙烯-马来酸酐-N-异丙基丙烯酰胺）（P（S-M-NIP））组成的囊泡，并功能化了 1,2-双（10,12-二十三碳二炔酰基）-sn-甘油-3-磷酸胆碱（DC PC）。基于 P（S-M-NIP）的温度敏感性和 DC PC 的光响应性，通过酶封装构建了一系列双重刺激响应纳米反应器，以调节其酶解效率。葡萄糖氧化酶封装的纳米反应器的动力学研究表明，在加热和紫外线（UV）照射下，其酶解速度分别提高了 2.1 倍和 1.6 倍。因此，研究了在包埋β-半乳糖苷酶和葡萄糖氧化酶的酶级联反应中。结果表明，在 UV 照射下改变环境温度可使酶解效率提高 2.9 倍。在酶级联反应中，双重刺激响应聚合物囊泡还可以消除 H2O2 的干扰。该囊泡具有开关膜通透性的潜力，而受限的微环境在温度变化和存在紫外光时对调节反应起着关键作用。我们的合成多细胞器样系统为通过编程纳米胶囊的“打开/关闭”状态来模拟级联反应催化过程的控制提供了一种新方法。
