Unraveling Ofloxacin Behavior in Aqueous Environments: Molecular Dynamics of Colloidal Formation and Surface Adsorption Mechanisms

Abstract

Ofloxacin, a commonly prescribed antibiotic, raises serious environmental concerns due to its persistence in aquatic systems. This study offers new insights into the environmental behavior of ofloxacin and its interactions with carbon-based adsorbents with the aim of enhancing our understanding of its removal mechanisms via adsorption processes. Using a comprehensive computational approach, we analyzed the speciation, pK_a values, and solubility of ofloxacin across various pH conditions, accounting for all four microspecies, including the often-overlooked neutral form. Our findings indicate that clustering of ofloxacin in water is influenced not only by solubility but also by electrostatic repulsion, dipole creation, and π-π interactions. At extreme pH levels, clustering is primarily driven by Coulombic forces and strong π-π interactions between different ofloxacin molecules. Density functional theory (DFT) was employed to optimize the molecular structures, and molecular dynamics (MD) simulations explored interactions among ofloxacin, water, and carbon surfaces. Hybrid Reverse Monte Carlo (HRMC) simulations were used to determine the disordered structure of an activated carbon cloth (ACC), specifically, KIP1200 (Dacarb company, France), for use in MD simulations. KIP1200 contains a small amount of oxygen (less than 2%), which supports our assumption of a predominantly carbon-based structure. Surface interactions were found to vary significantly depending on the ofloxacin form. The neutral form exhibited strong π-π interactions with flat surfaces, whereas the zwitterionic form displayed a greater affinity for curved surfaces. On KIP1200, adsorption was pH-dependent: acidic conditions enhanced adsorption due to reduced repulsion, while adsorption decreased under basic conditions. The aromatic rings in ofloxacin, combined with the high electronegativity of its fluorine atoms, played a critical role in facilitating adsorption through π-π interactions. These results deepen our understanding of ofloxacin microspecies, colloid formation, and adsorption mechanisms under diverse conditions.