Jiangsu Engineering Laboratory of Smart Carbon-Rich Materials and Device, Jiangsu Province Hi-Tech Key Laboratory for Bio-Medical Research, School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, China.
Medical School, Southeast University, Nanjing, 210009, China.
Nat Commun. 2023 May 15;14(1):2780. doi: 10.1038/s41467-023-38459-9.
Self-adaptability is highly envisioned for artificial devices such as robots with chemical noses. For this goal, seeking catalysts with multiple and modulable reaction pathways is promising but generally hampered by inconsistent reaction conditions and negative internal interferences. Herein, we report an adaptable graphitic CN-based copper single-atom catalyst. It drives the basic oxidation of peroxidase substrates by a bound copper-oxo pathway, and undertakes a second gain reaction triggered by light via a free hydroxyl radical pathway. Such multiformity of reactive oxygen-related intermediates for the same oxidation reaction makes the reaction conditions capable to be the same. Moreover, the unique topological structure of CuCN along with the specialized donor-π-acceptor linker promotes intramolecular charge separation and migration, thus inhibiting negative interferences of the above two reaction pathways. As a result, a sound basic activity and a superb gain of up to 3.6 times under household lights are observed, superior to that of the controls, including peroxidase-like catalysts, photocatalysts, or their mixtures. CuCN is further applied to a glucose biosensor, which can intelligently switch sensitivity and linear detection range in vitro.
自适应能力是高度期望的人工设备,如具有化学鼻子的机器人。为此,寻求具有多种和可调节反应途径的催化剂是有希望的,但通常受到不一致的反应条件和负内部干扰的阻碍。在此,我们报告了一种自适应的基于石墨 CN 的铜单原子催化剂。它通过结合的铜-氧途径驱动过氧化物酶底物的基本氧化,并通过光通过游离羟基自由基途径进行第二次增益反应。对于相同的氧化反应,这种多样的与活性氧相关的中间体使得反应条件能够相同。此外,CuCN 的独特拓扑结构以及专门的供体-π-受体连接体促进了分子内电荷分离和迁移,从而抑制了这两种反应途径的负干扰。结果,在家庭灯光下观察到良好的基础活性和高达 3.6 倍的优异增益,优于包括过氧化物酶样催化剂、光催化剂或它们的混合物的对照物。CuCN 进一步应用于葡萄糖生物传感器,该传感器可以在体外智能切换灵敏度和线性检测范围。