Spectroelectrochemical Analysis of Ion Transfer Mechanisms of Mitoxantrone at Liquid|Liquid Interfaces: Effects of Zwitterionic Dendrimer and Phospholipid Layer

The ionic partition property and transfer mechanism of the anthraquinone antitumor agent mitoxantrone (MTX) were studied in detail at the water|1,2-dichloroethane (DCE) interface by means of surface-sensitive spectroelectrochemical techniques. The interfacial mechanism of the cationic MTX species was composed of potential-driven ion transfer and adsorption processes. The ion association between MTX and zwitterionic polyamidoamine (PAMAM) dendrimers with peripheral carboxy groups was also investigated in terms of the effects of pH and dendritic generation. The monovalent HMTX+ interacted effectively with the negatively charged dendrimers at neutral pH, while the divalent H2MTX2+ exhibited a weak association under acidic conditions. The higher stability of the dendrimer–MTX associates in the interfacial region was found for higher dendritic generations: G3.5 ≥ G2.5 > G1.5. The interfacial behavior of MTX and its dendrimer associates was further analyzed at the phospholipid-modified interface as a model biomembrane surface. The adsorption process of HMTX+ occurred mainly on the hydrophilic side of the phospholipid layer. The spectroelectrochemical results indicated that the dendrimers penetrate into the phospholipid layer and alter the transfer mechanism of HMTX+ across the interface.