Exploring the Nature of the Nanocavity and Channels in Apoferritin and Apoferritin–Sodium Dodecyl Sulfate Complex Using an Enhanced Antenna Effect through the Encapsulation of EuIII–Tetracycline

Abstract

The drug tetracycline hydrochloride (TC), which has cytotoxic and cytostatic effects on tumor cells, has been encapsulated within the nanocavity of apoferritin in the form of its EuIII complex (Eu3TC). The Eu3TC complex was encapsulated within apoferritin through disassembly followed by reassembly of the protein and exhibited significantly enhanced EuIII emission in comparison with that of free Eu3TC in aqueous buffer at pH 8. The steady‐state and transient measurement of the emission of each species in the ternary system suggest that the effective sensitization of EuIII emission may be ascribed to a comparatively rigid environment for the bound TC after encapsulation that promotes efficient energy transfer to the EuIII ions. Emission studies in D2O revealed that the microenvironment of the EuIII ion is shielded from O–H oscillators in the ternary system, and the extent of shielding is greater after the encapsulation of the complex within the apoferritin cavity. The rotational correlation time (θc) of bound TC and docking studies also support the contention that the TC is in a more buried environment after encapsulation within the apoferritin cavity. A competition study with sodium dodecyl sulfate (SDS) revealed that SDS does not interfere with the binding of TC to apoferritin. The biocompatible system consisting of Eu3TC encapsulated within the cavity of apoferritin may be used as an efficient targeted drug transporter, and the sensitization of the EuIII emission may also enable its use as a biosensor.