Ding Ying, Liu Jianming, Pei Longsheng, Li Yuan, Duan Yaqin, Song Yonghai, Miao Longfei, Liu Limin, Wang Li
Nanofiber Engineering Center of Jiangxi Province, National Engineering Research Center for Carbohydrate Synthesis, Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, College of Chemistry and Materials, Jiangxi Normal University, 99 Ziyang Road, Nanchang, 330022, China.
Bioact Mater. 2025 Jun 19;52:623-633. doi: 10.1016/j.bioactmat.2025.06.026. eCollection 2025 Oct.
Enzyme biosensors, despite their high specificity and sensitivity, are constrained by the inherent fragility of enzymes. Despite being considered ideal for enzyme protection by in-situ covalent organic frameworks (COFs) immobilization, the harsh conditions of COFs synthesis often lead to enzyme inactivation. Herein, a strategy was developed to prepare robust enzyme@COFs microcapsules (enzyme@MC) by the interfacial assembly of hydrophobic COFs spheres to form stable Pickering emulsions, followed by COFs regrowth to reinforce the microcapsules. Compared with conventional methods, this approach confines the enzymes in a mild environment, achievig an impressive encapsulation efficiency of 85.9 %. Enzymes are protected from inhospitable conditions by the mechanical robustness of microcapsules COFs shell which also features adjustable pores to enhance substrate transport and exhibit size selectivity. The success of strategy was verified by the construction of enzyme@MC based on various hydrophobic COFs spheres (water contact angle>90°) with different pore sizes and degrees of functionalization, and they can be pre-modified to meet specific application requirements. The strategy is simple yet effective. COFs employed in this strategy only requires a slight degree of hydrophobicity, rather than specific functional groups. In addition, a formula was also proposed to predict and control the size of the enzyme@MC accurately. A cascade catalytic system based on enzyme@MC has been emulated for the construction of a colorimetric and electrochemical glucose biosensing platform. This study provides new insight into the construction of enzyme@MC and their biosensing applications.
酶生物传感器尽管具有高特异性和高灵敏度，但受酶固有脆弱性的限制。尽管原位共价有机框架（COF）固定化被认为是保护酶的理想方法，但COF合成的苛刻条件常常导致酶失活。在此，我们开发了一种策略，通过疏水COF球的界面组装形成稳定的皮克林乳液，进而制备坚固的酶@COF微胶囊（酶@MC），随后进行COF再生长以强化微胶囊。与传统方法相比，这种方法将酶限制在温和的环境中，实现了高达85.9%的令人印象深刻的包封效率。微胶囊的COF壳具有机械稳健性，可保护酶免受恶劣条件影响，其还具有可调节的孔隙，以增强底物传输并表现出尺寸选择性。通过基于具有不同孔径和功能化程度的各种疏水COF球（水接触角>90°）构建酶@MC，验证了该策略的成功，并且它们可以进行预修饰以满足特定应用要求。该策略简单而有效。此策略中使用的COF仅需要轻微的疏水性，而非特定的官能团。此外，还提出了一个公式来准确预测和控制酶@MC的尺寸。基于酶@MC的级联催化系统已被模拟用于构建比色和电化学葡萄糖生物传感平台。本研究为酶@MC的构建及其生物传感应用提供了新的见解。
