School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang, 212013, Jiangsu Province, China.
School of Food and Biological Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang, 212013, Jiangsu Province, China.
Colloids Surf B Biointerfaces. 2021 Dec;208:112099. doi: 10.1016/j.colsurfb.2021.112099. Epub 2021 Sep 15.
Encapsulating enzyme within MOF (enzyme-MOF) gives rise to new opportunity to improve the fragility of enzyme, but practical application of enzyme-MOF composite is far from being realized. The development of a novel enzyme-MOF composite system should simultaneously guarantee the enhanced activity and controllably complete recycling, and only in this way can we efficiently and economically utilize the enzyme-MOF composite. Herein, we addressed all these fundamental limitations of current enzyme-MOF composite by establishing aptamer-functionalized enzyme-MOF composite (HRP-ZIF-8@P1). HRP-ZIF-8@P1 relied on automatic structure switch of aptamer-target binding and aptamer-cDNA (complementary DNA) hybridization, achieving effectiveness in self-enriching substrate around HRP-ZIF-8@P1 to boost enzymatic activity first, subsequently hybridizing spontaneously with magnetically controllable cDNA sequence (FeO@P3) to completely recover the HRP-ZIF-8@P1, where preferentially capturing substrate could further induce the release of the hybridized HRP-ZIF-8@P1 for automatically starting the cyclic enzyme catalysis. A 5.6-fold enhancement in the catalytic efficiency for BPA degradation was endowed, and 94.7% catalytic activity was retained for 8 consecutive degradations of BPA, both of which were even more significant than HRP-ZIF-8. Additionally, remarkable stability of HRP-ZIF-8@P1 was afforded by dual-layer protection of ZIF-8 and P1 in denaturing conditions. Taking the possibility of discovering an aptamer for any target into account, the aptamer-functionalized enzyme-MOF composites provide a generic and simple guide for simultaneously boosting enzymatic activity and controllably full recycling the enzyme-MOF systems, accelerating their commercial utilizations.
将酶包裹在金属有机骨架（MOF）中为提高酶的脆弱性提供了新的机会，但酶-MOF 复合材料的实际应用还远未实现。新型酶-MOF 复合材料体系的发展应同时保证增强的活性和可控的完全回收，只有这样，我们才能有效地、经济地利用酶-MOF 复合材料。在此，我们通过建立适体功能化酶-MOF 复合材料（HRP-ZIF-8@P1）解决了当前酶-MOF 复合材料的所有这些基本限制。HRP-ZIF-8@P1依赖于适体-靶结合和适体-cDNA（互补 DNA）杂交的自动结构切换，实现了在 HRP-ZIF-8@P1 周围自动富集底物的有效性，从而首先提高酶活性，随后与可磁控的 cDNA 序列（FeO@P3）自发杂交，完全回收 HRP-ZIF-8@P1，其中优先捕获底物可进一步诱导杂交 HRP-ZIF-8@P1 的释放，从而自动启动循环酶催化。BPA 降解的催化效率提高了 5.6 倍，BPA 的 8 次连续降解中保留了 94.7%的催化活性，这两个指标都比 HRP-ZIF-8 更为显著。此外，在变性条件下，ZIF-8 和 P1 的双层保护赋予了 HRP-ZIF-8@P1 显著的稳定性。考虑到发现任何目标适体的可能性，适体功能化酶-MOF 复合材料为同时提高酶的活性和可控地完全回收酶-MOF 系统提供了一种通用且简单的指导，加速了它们的商业应用。
