In this work, we develop a new type of mesoporous 2D N, B, and P codoped carbon network (NBP-CNW) arranged into high-order 3D nanotube arrays (NTAs), which are wrapped onto a flexible carbon fiber microelectrode, and this microelectrode is employed as a high-performance carbon-based nanocatalyst for electrochemical biosensing. The NBP-CNW-NTAs synthesized by a facile, controllable, ecofriendly and sustainable template strategy using ionic liquids as precursors possess a high structural stability, large surface area, abundant active sites, and effective charge transport pathways, which dramatically improve their electrocatalytic activity and durability in the redox reaction of cancer biomarker H2O2. Benefiting from these unique structural merits, superb electrochemical activity and good biocompatibility, the NBP-CNW-NTAs-modified microelectrode demonstrates excellent sensing performance toward H2O2 and is embedded in a homemade microfluidic electrochemical biosensor chip for the real-time tracking of H2O2 secreted from different live cancer cells with or without radiotherapy treatment, which provides a new strategy for distinguishing the types of cancer cells and evaluating the radiotherapeutic efficacy of cancer cells. Furthermore, the functional microelectrode is integrated into an implantable probe for the in situ detection of surgically resected human specimens to distinguish cancer tissues from normal tissues. These will be of vital significance for cancer diagnoses and therapy in clinical practice.
The development of nanohybrid with high electrocatalytic activity is of great significance for electrochemical sensing applications. In this work, we develop a novel and facile method to prepare a high-performance flexible nanohybrid paper electrode, based on nitrogen-doped carbon (NC) wrapped Bi nanoparticles (Bi-NPs) assembly derived from Bi-MOF, which are decorated on a flexible and freestanding graphene paper (GP) electrode. The as-obtained Bi-NPs encapsulated by an NC layer are uniform, and the active sites are increased by introducing a nitrogen source while preparing Bi-MOF. Owing to the synergistic effect between the high conductivity of GP electrode and the highly efficient electrocatalytic activity of Bi-NPs, the NC wrapped Bi-NPs (Bi-NPs@NC) modified GP (Bi-NPs@NC/GP) electrode possesses high electrochemically active area, rapid electron-transfer capability, and good electrochemical stability. To demonstrate its outstanding functionality, the Bi-NPs@NC/GP electrode has been integrated into a handheld electrochemical sensor for detecting heavy metal ions. The result shows that Zn2+, Cd2+, and Pb2+ can be detected with extremely low detection limits, wide linear range, high sensitivity, as well as good selectivity. Furthermore, it demonstrates outstanding electrochemical sensing performance in the simultaneous detection of Zn2+, Cd2+, and Pb2+. Finally, the proposed electrochemical sensor has achieved excellent repeatability, reproducibility, stability, and reliability in measuring real water samples, which will have great potential in advanced applications in environmental systems.
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