Shi Jiafu, Wang Xiaoli, Zhang Shaohua, Tang Lei, Jiang Zhongyi
School of Environmental Science & Engineering, Tianjin University, Tianjin 300072, P. R. China.
J Mater Chem B. 2016 Apr 21;4(15):2654-2661. doi: 10.1039/c6tb00104a. Epub 2016 Mar 31.
In this study, a proof-of-concept for constructing efficient and stable biocatalysts is reported for biphasic catalytic reactions, where enzyme-conjugated ZIF-8 particles are utilized as efficient and stable Pickering interfacial biocatalysts. During the preparation of enzyme-conjugated ZIF-8 particles, dopamine modification on the surface of ZIF-8 particles is an essential step, which cannot only manipulate the surface hydrophilicity of ZIF-8 particles but also render surface reactive groups for conjugating enzymes in a green manner. The enzyme-conjugated ZIF-8 particles can be spontaneously assembled at the water/oil interfaces through optimizing their surface hydrophilicity, which then leads to enhanced catalytic activity as a result of much lower external and internal diffusional resistances. Such Pickering interfacial catalysts can be simply recycled and positioned at the water/oil interface via relatively low-speed centrifugation (5000 rpm), thus indicating an ease of separation for the substrate (p-NPP in the oil phase), the product (p-NP in the water phase) and catalysts (as the solid phase). Moreover, as evidenced by a 13-cycle reaction and a 37 day storage test, the robust conjugation of an enzyme on the surface of the particles can effectively protect the enzyme from the organic-solvent stress, thus retaining high catalytic activity.
在本研究中,报道了一种用于双相催化反应构建高效稳定生物催化剂的概念验证,其中酶共轭的ZIF-8颗粒被用作高效稳定的Pickering界面生物催化剂。在酶共轭ZIF-8颗粒的制备过程中,ZIF-8颗粒表面的多巴胺修饰是关键步骤,这不仅能控制ZIF-8颗粒的表面亲水性,还能以绿色方式提供用于共轭酶的表面反应基团。通过优化其表面亲水性,酶共轭的ZIF-8颗粒可在水/油界面自发组装,由于外部和内部扩散阻力大大降低,从而导致催化活性增强。这种Pickering界面催化剂可通过相对低速离心(5000 rpm)简单回收并定位在水/油界面,因此表明底物(油相中的对硝基苯酚磷酸酯)、产物(水相中的对硝基苯酚)和催化剂(作为固相)易于分离。此外,如13次循环反应和37天储存测试所证明的,颗粒表面酶的牢固共轭可有效保护酶免受有机溶剂胁迫,从而保持高催化活性。