Surfactant systems have been frequently used as pseudomodels for investigating interactions of drugs with biological membranes because of their structural similarities with the latter. This helps to understand complicated yet very important biological processes like diffusion of bioactive moieties through biomembranes. The current study deals with voltammetric and spectroscopic studies to evaluate the interaction of a potential antibacterial drug, gatifloxacin (GTF), with a cationic surfactant, dodecyltrimethylammonium bromide (DTAB), and an anionic surfactant, sodium dodecyl sulfate (SDS), under physiological conditions (phosphate buffer, pH 7.4). For more detailed insight into the GTF–ionic surfactant interactions, density and acoustic data were also recorded and used to calculate several important parameters, namely, apparent molar volume (ɸV), isentropic compressibility (Ks), and apparent molar isentropic compressibility (ɸK) at T = 298.15, 303.15, 308.15, and 313.15 K. Values for partial molar volume (ɸVofalse), partial molar expansivity ()ɸEo, specific acoustic impedance (Z), relative association (RA), intermolecular free length (Lf), and sound velocity number (U) were also obtained. The interpretation of the concentration dependence of the above‐mentioned quantities using a cosphere overlap model led to a better apprehension of solute–solute and solute–solvent intermolecular interactions present in the investigated system, whereas cyclic voltammetry and ultra violet (UV)–visible spectroscopic studies assisted in predicting the location of adsorbed GTF molecules within the DTAB and SDS micelles.
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