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In this review, recent research efforts that aimed at developing nanopore sensors for detection of metal ions, which play a crucial role in environmental safety and human health, are highlighted. Protein pores use three stochastic sensing‐based strategies for metal ion detection. The first strategy is to construct engineered nanopores with metal ion binding sites, so that the interaction between the target analytes and the nanopore can slow the movement of metal ions in the nanochannel. Second, large molecules such as nucleic acids and especially peptides can be utilized as external selective molecular probes to detect metal ions based on the conformational change of the ligand molecules induced by the metal ion–ligand chelation/coordination interaction. Third, enzymatic reactions can also be used as an alternative to the molecule probe strategy in the situation that a sensitive and selective probe molecule for the target analyte is difficult to obtain. On the other hand, by taking advantage of steady‐state analysis, synthetic nanopores mainly use two strategies (modification and modification‐free) to detect metals. Given the advantages of high sensitivity and selectivity, and label‐free detection, nanopore‐based metal ion sensors should find useful application in many fields, including environmental monitoring, medical diagnosis, and so on.

 

We report a label-free nanopore sensor for the detection of Zn 2+ ions. By taking advantage of the cleavage of a substrate peptide by zinc-dependent enzymes, nanomolar concentrations of Zn 2+ ions could be detected within minutes. Furthermore, structurally similar transition metals such as Ni 2+ , Co 2+ , Hg 2+ , Cu 2+ , and Cd 2+ did not interfere with their detection. The enzymatic reaction-based nanopore sensing strategy developed in this work may find potential applications in environmental monitoring and medical diagnosis. 

A disintegrin and metalloproteinase 17 (ADAM17) has become a novel biomarker and potential therapeutic target for the early detection and treatment of human cancers. In this work, by covalently attaching fluorescently labeled ADAM17 substrate peptide (Pep-FAM) molecules to carboxylated graphene oxide (cGO) and monitoring the cleavage of the peptide substrate by ADAM17, we developed a cGO-Pep-FAM fluorescence sensor for the rapid, sensitive and accurate detection of ADAM17. The sensor was highly sensitive with a detection limit of 17.5 picomolar. Furthermore, the sensor was selective: structure similar proteases such as ADAM9 and MMP-9 would not interfere with ADAM17 detection. In addition, simulated serum samples were successfully analyzed. Our developed cGO-Pep-FAM sensing strategy should find useful applications in disease diagnosis and drug screening. 

To overcome the effect of other components of complicated biological samples on nanopore stochastic sensing, displacement chemical reaction was utilized to selectively extract the target nucleic acid from whole blood. Given its simplicity and high sensitivity for detecting nucleic acids, our developed displacement chemistry-based nanopore sensing strategy offers the potential for fieldable/point-of-care diagnostic applications.