Electrocatalytic Imprinted Polymer of N-Doped Hollow Carbon Nanosphere-Palladium Nanocomposite for Ultratrace Detection of Anticancer Drug 6-Mercaptopurine.

In this work, a nanohybrid-based imprinted polymer consisting of N-doped hollow carbon nanospheres and palladium is reported for the electroanalysis of ultratrace level of anticancer drug, 6-mercaptopurine, used in the treatment of leukemia. For this, N-doped carbon nanospheres decorated with palladium were first developed, and subsequently, a molecular imprinted polymer layer was grown onto their surfaces. The so-produced silica-embedded nanocomposite was made hollow by etching silica moieties with hydrofluoric acid. Finally, the whole system was doped on an ionic-liquid-modified pencil graphite electrode. The underlying synergistic effect of hollow carbon nanosphere-supported palladium nanoparticles inculcated electrocatalytic action. Notably, all rebinding sites in solid core-shells were confined within the shell, which hampers the effective diffusion of template. However, in this work, an effective diffusion of template across the hollow structure of inner and outer surfaces was observed. Consequently, this rendered approximately 2-fold heterogeneous rate constant as compared to the solid core-shell-based sensor. Differential pulse voltammetric transduction was used for ultratrace detection of 6-mercaptopurine through anodic stripping method. The hollow imprinted sensor revealed a linear dependence of current with concentration range 0.80-70.748 ng mL. The limits of detection 0.11-0.22 ng mL were realized in water, human blood plasma, urine, and pharmaceuticals. Thus, the proposed sensor demonstrated an attractive sensitivity reproducibility, as well as endurance requisite for the treatment of leukemia patients.