We are just beginning to exploit the fascinating potential of thionine, called electrochemical probe that can selectively recognize specific polycyclic aromatic hydrocarbons (PAHs), as tools for the detection of tricyclic aromatic hydrocarbons phenanthrene (PHE) and anthracene (ANT). A novel electrochemical sensing platform by modification of electroactive thionine functionalized graphene onto glass carbon electrode (Th/GRs/GCE) surface was constructed. The immobilized thionine showed a remarkable stability, which may benefit from the π-π stacking force with graphene. Under optimum conditions, the proposed electrochemical sensor exhibited high sensitivity and low detection limit for detecting PHE and ANT. The total amount of PHE and ANT could be quantified in a wide range of 10pM-0.1μM with a good linearity (R(2)=0.9979) and a low detection limit of 0.1pM (S/N=3). Compounds which possess one or two benzene rings or PAHs with more than three rings, such as benzene, naphthalene (NAP), benzo[a]pyrene (BaP) and pyrene (PYR) show little interference on the detection. Consequently, a simple and sensitive electrochemical method was proposed for the determination of PHE and ANT, which was used to determine PHE and ANT in waste water samples. The electrochemical method provides a general tool that complements the commonly used spectroscopic methods and immune method for the detection of PAHs.
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