School of Chemical Engineering and Technology, Sun Yat-sen University, 519082, Zhuhai, China.
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, 510275, Guangzhou, China.
Nat Commun. 2023 Jun 20;14(1):3644. doi: 10.1038/s41467-023-39364-x.
Rational integration of native enzymes and nanoscaffold is an efficient means to access robust biocatalyst, yet remains on-going challenges due to the trade-off between fragile enzymes and harsh assembling conditions. Here, we report a supramolecular strategy enabling the in situ fusion of fragile enzymes into a robust porous crystal. A c2-symmetric pyrene tecton with four formic acid arms is utilized as the building block to engineer this hybrid biocatalyst. The decorated formic acid arms afford the pyrene tectons high dispersibility in minute amount of organic solvent, and permit the hydrogen-bonded linkage of discrete pyrene tectons to an extended supramolecular network around an enzyme in almost organic solvent-free aqueous solution. This hybrid biocatalyst is covered by long-range ordered pore channels, which can serve as the gating to sieve the catalytic substrate and thus enhance the biocatalytic selectivity. Given the structural integration, a supramolecular biocatalyst-based electrochemical immunosensor is developed, enabling the pg/mL detection of cancer biomarker.
将天然酶与纳米支架进行合理整合是获得稳健生物催化剂的有效手段，但由于脆弱酶与苛刻组装条件之间的权衡，这仍然是一个持续的挑战。在这里，我们报告了一种超分子策略，使脆弱的酶能够原位融合到坚固的多孔晶体中。我们利用具有四个甲酸臂的 c2 对称的芘作为构建模块来设计这种杂化生物催化剂。修饰后的甲酸臂使芘在少量有机溶剂中具有高分散性，并允许离散的芘在几乎无有机溶剂的水溶液中通过氢键连接到酶周围的扩展超分子网络上。这种杂化生物催化剂被长程有序的孔道覆盖，这些孔道可以作为筛子来筛选催化底物，从而提高生物催化选择性。鉴于结构的整合，我们开发了一种基于超分子生物催化剂的电化学免疫传感器，能够实现对癌症生物标志物的 pg/mL 检测。
