Sensitive Hydrazine Electrochemical Biosensor Based on a Porous Chitosan-Carbon Nanofiber Nanocomposite Modified Electrode

A novel electrochemically-based biosensor was developed for the determination of hydrazine by modifying a glassy carbon electrode with an aqueous dispersion of carboxylic group-functionalized carbon nanofiber/chitosan solution, and then absorbing hemoglobin on the surface of chitosan-carbon nanofibers. Nafion was used to coat the hemoglobin membrane. The interactions of hemoglobin and the nafion/chitosan-carbon nanofibers were investigated by ultraviolet-visible absorption, infrared, and circular dichroism spectroscopies. The results indicated that the native structure of hemoglobin was retained post-immobilization. The circular dichroism results showed that the alpha-helical structure of hemoglobin was preserved though a small change was observed in the presence of the nafion/chitosan-carbon nanofibers. The modified nanofibers were further characterized by scanning electron microscopy, electron impendence spectroscopy, and cyclic voltammetry. The electrocatalytic mechanism of hemoglobin to the oxidation of hydrazine was investigated and an irreversible diffusion-controlled electrode process was obtained. The electron transfer rate constant (k(s)), transfer coefficient (alpha), and Michaelis-Menten constant (K-m) were also evaluated. The peak current of the catalytic oxidation was linear with hydrazine concentration from 3.722x10(-5) to 1.601x10(-3) molar with a correlation coefficient of 0.995. The detection limit was estimated to be 2.7 micromoles per liter. The sensitivity, stability, and reproducibility of the nafion/hemoglobin/chitosan-carbon nanofiber/glassy carbon electrode for the oxidation of hydrazine were also investigated.